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Industrial production in the United States has been holding steady for the past few months. The latest figures are encouraging, with a 0.6% improvement in June, but it is too early to treat this as an uptrend. Industrial production currently accounts for 19% of U.S. GDP and is a good leading indicator of the economic cycle. It is particularly useful in identifying when the economy turns a corner and starts expanding or, alternatively, contracting.
When industrial production dropped sharply at the end of 2015 and in early 2016, investors saw this as a possible sign of recession. But the slowdown was really caused by the collapse in oil prices and energy production. This explained the poor industrial production figures and provided reassurance that the rest of the economy would not be affected. Indeed, the economy continued to be powered by the services sector, itself buoyed by high consumer spending.
The breakdown of industrial production by market group is a fair reflection of the strengths and weaknesses of the US economy:
Construction supplies has expanded by an average of 1.4% year on year since the start of 2016, in step with growth in the property sector over the same period. This group only accounts for 5% of total industrial production, however.
Consumer goods, which includes automobiles, electronics and food and represents 30% of total industrial production, has been expanding at an average pace of 68% year on year since the start of 2016. Automobile manufacturing (+7.4%) has been particularly strong. Again, these figures are in line with solid consumer spending, which is driving domestic growth.
On the other hand, business equipment and defence & space equipment – 14% of total production – have struggled in 2016. This is mainly due to very low capacity utilisation, around 75.4%. Demand is simply not strong enough to keep companies operating at full productive capacity, and this puts a damper on their need for machines and other capital goods. Weak demand for capital goods is also a result of increased spending by firms on intangible capital, including IT systems, technological progress (the cloud, cyber security), organisational knowledge and R&D. It is hard to quantify spending on intangible capital, but a number of papers published by the Federal Reserve suggest that it is approximately equal to spending on fixed capital.
With machinery orders down and exports hurt by the strong dollar, business equipment is likely to bring down overall industrial production figures.
Finally, energy materials (including oil and gas) and non-energy materials for intermediate goods are sharply down year on year. This owes largely to the pullback in oil production. These two sectors account for 45% of total industrial production and weighed heavily on the overall figures. That said, some companies in the energy sector will ramp up production following the recent rise in oil prices. Initial signs of this are apparent in the latest production figures and rig count.
 Corrado, Hulten and Sichel, ”Intangible Capital and U.S. Economic Growth”, 2009
We expect capital spending to grow by only 1.8% on average in 2016 (versus +4.1% in 2015). The impact on orders for capital goods will weigh further on total industrial production.
Industrial production is more likely to find support in rising (or even stable) energy prices. This, along with the strength of consumer goods and construction supplies, could help push the overall year-on-year figure back into positive territory before the end of 2016.


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Tag Archives: grand canyon hiking tours
The Grand Canyon is a vacation destination for many people as it is one of America’s most beautiful natural attractions. As a result, many have wanted to explore the areas around the Grand Canyon. The area has many great hiking trails you will enjoy.
Before you go hiking, it’s important you have the correct hiking equipment. A familiarity with the areas’ topography is great to know which trail hiking shoes to take with you.

domain: geography


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The Tobago Youth Council (TYC) is urging the authorities to ensure that all international passengers entering the island adhere to all covid19 travel protocols.
On Monday, British Airways is expected to resume flights to Tobago, almost two years after the country shut its borders to prevent the spread of the virus. Dutch airline Virgin Atlantic is scheduled to resume flights to the island on January 29.
TYC president Janae Campbell said while the council supports the return of international flights to Tobago, it is deeply concerned about the management of international travellers.
“We advocate for proactive, precautionary measures to be implemented in keeping with the covid19 travel protocols,” she told Newsday. “We would like persons to be tested adequately before entering the country and upon arrival, there should be testing mechanisms in practice.”
Campbell said the council also wants passengers quarantined on arrival “in order to foster a level of prudence and security.”
She said it would also like antigen tests to be accepted as a viable method of detection of covid19.
“While rapid antigen tests are not as accurate as PCR tests, there is still a high measure of accuracy.”
Campbell said the benefits to be derived from using rapid testing include cheaper costs and convenience.

domain: travel


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Preparing Pre-Service Teachers To Manage Behavior Problems in the Classroom: The Feasibility and Acceptability of Using a Mixed-Reality Simulator
Developing Knowledge about What Works for Make Schools Safe: Implementation and Evaluation of Tools for Life in Jackson Public School District in Mississippi
Preliminary Evaluation of the Implementation of the Problem Solving Training and Offence Behaviour Program in Community Corrections and Prisons Across Victoria, Australia (From Policing in Central and Eastern Europe: Dilemmas of Contemporary Criminal Justice, P 505-517, 2004, Gorazd Mesko, et al., e
Taking Stock: An Overview of NIJ's Reentry Research Portfolio and Assessing the Impact of the Pandemic on Reentry Research
Over several decades, the National Institute of Justice (NIJ) has made significant contributions to the field of reentry, specifically what works for whom and when. In recent years, however, the global pandemic has made it increasingly difficult to conduct research on and with populations involved with the justice system. During this time, many researchers assessing various justice-related outcomes were unable to continue their inquiries as planned due to a lack of access to their populations of interest, forcing many to pivot and rethink their research designs.

domain: sociology


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Brett Templeman is a native of Ventura County and a graduate of the University of Colorado at Boulder and the University of San Diego – School of Law.
Brett began practicing law in 2003 and has personally tried many court and jury trials, achieving numerous multimillion dollar trial verdicts, arbitration awards and settlements for his clients. He is the Past President of Ventura County Trial Lawyers Association (VCTLA) and is an active member of the 2017 Ventura County Bar Association (VCBA) and the Consumer Attorneys of California (CAOC). In 2013 he was nominated for the VCTLA’s Trial Lawyer of the Year Award. While the majority of his cases are within the Counties of Ventura and Santa Barbara, he has handled hundreds of cases throughout the State of California, including federal court.
Brett dedicates the bulk of his practice to helping people and businesses who have suffered harm due to the misconduct of others. He specializes in the following areas: personal injury; wrongful death; employment law; and real property damage cases stemming from flood and fire.
Brett is a lifelong waterman and former World Champion Bodysurfer. He lives in Ojai with his wife and daughter.

domain: law


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One of the top travel destinations in the Arabian world, Rabat is only the third largest city of Morocco but nevertheless it's the most important in terms of administration and tourism.
The main sights of the city are:
- The mausoleum of Mohammed V. Completed in 1971 it serves as a tomb to Mohammed V, a former sultan of Morrocco and his his two sons, late King Hassan II and Prince Abdallah. The building is a masterpiece of late Islamic architecture.
- The ruins of Chellah situated at the outskirts of the city. This is a complex of ruins of an ancient roman town that continued to develop until the middle ages.
- The old gates to the city: Bab Oudaïa, Bab El-Had and Bab-Rouah.


Social Media and Its Impact on Loneliness
The science behind loneliness and whether social media can be the perfect cure for this social dilemma
Human beings are social creatures that thrive on social interactions with other fellow human beings. Building and maintaining quality relationships with others is a vital component for the development of positive mental health and wellbeing. Any lack of social contact with other people can only serve to increase feelings of loneliness, which is a known risk factor for the development of common mental health disorders (e.g., depression, anxiety).
One study, which surveyed young people across care systems in both Finland and England, found that those who reported having strong social support networks also reported having higher mental wellbeing compared to those who reported having no such networks of support.
Now that we live in the age of social media, human beings no longer need to be in each other’s presence to exchange conversations and interact with one another. Therefore, it would seem plausible to think that social media use could compensate for any lack of in-person social interactions and reduce feelings of loneliness.
In this story, we will examine what loneliness is, exactly how social media affects loneliness and whether or not social media can be a useful cure for this problem or if real in-person social interactions are a better course of treatment.
Definition of loneliness
In order to understand an individual’s experience of loneliness, it is important to consider the very definition of loneliness and how it affects a person’s health and wellbeing. When studying loneliness, it is important to draw a distinction between the objective experience of being alone and the subjective experience of feeling lonely.
This is because a person who spends a lot of time on their own may enjoy doing so and not feel lonely as a result while others may spend a lot of time in the presence of other people without feeling included within their social group/s and thus end up feeling lonely.
There are a range of factors that can contribute to the development of this feeling. Separation, divorce, family neglect/abuse and mental health issues are just a few examples of factors that can increase ones feelings of loneliness. As mentioned before, loneliness can serve as a risk factor for the development of mental health disorders, but more surprisingly, it can also contribute to the development of physical health disorders too.
A study in Switzerland found that, higher levels of loneliness was associated with an increased risk of developing serious physical health problems such as cancer, heart disease, stroke, diabetes and high levels of cholesterol as well as mental health problems such as depression and anxiety.
Moreover, it should come as no surprise that these effects were more pronounced in older adults than younger adults. However, what can come as a surprise is that loneliness is considered to be just as lethal as smoking. One study in India, found that loneliness contributes to rates of premature death and mortality on an equal level to smoking 15 cigarettes per day.
As such, loneliness has been identified by governments and health institutions as a serious public health issue that needs combating through various interventions to promote positive health and wellbeing among citizens.
Social media and its effect on loneliness
Many people will often use social media sites to cure themselves of loneliness, but social media use may not be as effective of an intervention as many people are led to believe.
Examination of scientific research into the relationship between social media use and loneliness shows that social media use does not have the curing effects on loneliness that many socially isolated users seek. Instead, the effects have been shown to work in the opposite direction, meaning social media use actually increases a person’s state of loneliness.
An American study among a group of young adults aged 19–32 years old examined the link between their social media use and perceived social isolation. The findings revealed that high social media use was significantly associated with strong feelings of perceived social isolation, thus suggesting that high social media use only serves to heighten a young person’s feelings of loneliness.
Considering the scale of this problem, it is clear to see why many health experts may label social media addiction as a disorder, even though it has not been officially classified as one by the World Health Organization (WHO) or the Diagnostic and Statistical Manual of Mental Disorders (DSM 5).
According to the American Addiction Center, social media use disorder is characterized as being “overly concerned about social media, driven by an uncontrollable urge to log on to or use social media, and devoting so much time and effort to social media that it impairs other important life areas”.
One country that uses this term frequently to describe such individuals is Lebanon. Social media use in Lebanon is extremely high and the country also has some very high rates of loneliness. A study was conducted there to examine the relationship between social media use disorder and loneliness and to better understand the magnitude and scope of this problem within Lebanese society.
The study found that high social media use disorder, along with high levels of insomnia and alexithymia were associated with increased feelings of loneliness among Lebanese people. More worryingly though, 23.7% of participants in this survey were characterized as having this disorder, a trend that if generalized to the wider Lebanese population, would implicate a significant health concern for citizens and health officials in the country.
Therefore, the use of social media as an alternative to in-person social interactions for reducing feelings of loneliness may not be a wise choice. However, there are a range of other useful interventions that can be used to tackle loneliness. Perhaps the most obvious one being to increase the number of in-person social interactions that one has with others.
Research in China has shown that while internet connection is not associated with an enhanced quality of life, in-person social interactions are and this has implications for reducing loneliness and improving social connectivity. Other research has also found that in-person social interactions foster a strong sense of closeness and self-disclosure which is not offered through digital communication.
However, despite these benefits, expanding one’s social network and increasing one’s opportunities for in-person social interactions may be of greater difficulty for some individuals than others.
Socially disadvantaged individuals in this respect, who often feel lonely, can benefit from participating in various programmes and schemes that are useful for addressing loneliness such as social skills training, local community groups and befriending support services.
Measures like these can help reduce their feelings of loneliness either by increasing opportunities for in-person interactions or by providing a strong sense of connectedness and social support. Therapy and counselling services can also be useful for tackling feelings of loneliness and helping lonely patients reflect on their subjective experience of feeling lonely and providing useful strategies to combat this feeling.
The impact of the coronavirus pandemic on loneliness
If any discussions concerning the nature of loneliness and social media use are to be held at this current time, it would be unreasonable not to explore the impact that the coronavirus pandemic has had on people’s state of loneliness and their usage of social media. Globally, the coronavirus pandemic has entailed a series of tough measures that have restricted our contact with friends and family members living within different households.
As a consequence, you would expect these restrictions would only serve to increase a person’s feelings of loneliness and prompt a higher usage of social media streams to maintain contact with others and research has found this to be the case.
In terms of the pandemic’s impact on loneliness, a survey in the UK found that loneliness was 27% prevalent during the first lockdown period in early 2020. Furthermore, the results showed this prevalence to be more pronounced in young adults compared to any other age group.
This finding could most likely be attributed to the fact that older age adults tend to have less contact with others compared to younger adults and, as such, restrictions on social contact for younger adults require greater adjustment than what they would for older age groups.
As for social media use, a market research agency in the UK found that social media use increased by 61% globally during the first phase of the pandemic with WhatsApp showing the highest increase (41%).
Therefore, loneliness is just another one of many epidemics that has occurred as a direct result of the pandemic and people have resorted to social media to maintain contact with others and compensate for the lack of opportunities to socialize with family and friends. However, the effects of social media use on feelings of loneliness were not equally distributed among individuals of different age groups.
By initial surprise, one study found that increased social media use was associated with higher feelings of loneliness in younger adults, the most affected by the loneliness pandemic, but lower feelings of loneliness in older adults, the least affected group, during the pandemic. One may believe that the most affected group, in this case, young adults, would benefit most from alternatives to in-person social interactions in an attempt to cure or suppress feelings of loneliness, but this wasn’t found to be the case.
Explanations for this finding are subject to individual interpretation but the most likely explanation could be that social media use may well have caused young adults to grieve over the loss of in-person interactions they would have frequently had with others in a pre-pandemic world. This means interventions that seek to reduce loneliness in young adults should be prioritized during pandemics but any adverse impacts on older adults should not be neglected.
Therefore, some of the aforementioned strategies that can be utilized in a coronavirus pandemic to reduce loneliness such as social skills training, therapy and counselling services are useful tools for coping with this problem in a period of social isolation.
Moreover, because loneliness is an emotion of social disconnectedness that can even be felt by individuals with a lot of social contact, pandemics can be a useful opportunity for such individuals to prioritize improving and enhancing the quality of relationships with family and others living within their households.
Research has shown that families who commit to spending quality time together are much happier than families who spend a lot of time apart.
In addressing the title of this story by reference to the research presented, social media is not the cure for dealing with feelings of loneliness and social isolation. In fact, social media seems to be making us feel more disconnected than connected, which is an opposite effect to what social media was created for and this problem has heightened as a direct consequence of the coronavirus pandemic.
Therefore, in seeking interventions and strategies to reduce loneliness, one must prioritize increasing their opportunities for in-person social interactions and improve the quality of their current relationships with others.
Of course, social media can be a useful way to maintain contact with family and friends, particularly during a restricted pandemic, and can be beneficial if used in conjunction with having regular in-person interactions with others. However, it should not be used excessively or as a substitute for spending time with others in their physical presence.
With scientists optimistic of the end of the pandemic being in sight, hopefully this means the end of the loneliness pandemic is in sight too and opportunities to connect and interact with others face-to-face will last an eternity.
Given the uncertainties pandemics are capable of creating, now is a great time to capitalize on these opportunities to socialize face-to-face with family and friends before they are potentially taken away from us in a short period of time at an unprecedented level.
I hope you found this story to be helpful in allowing you to understand what loneliness is and what steps you can take to overcome this feeling. If loneliness is an emotion you experience frequently and this story resonates with you, then please feel free to use the responses section below to share your experiences of loneliness and what strategies you have used to cope with it.
Instead of using social media to cope with loneliness, I also hope this story has encouraged you to develop the confidence and motivation to meet people in-person and build new or rekindle existing relationships with others and to share in the joy of having meaningful social interactions in each other’s presence.
About the Creator
My passion is to write stories related to the topics of psychology and mental health | (Bsc) Hons Applied Psychology Student at Glasgow Caledonian University 😁
Very well written. Keep up the good work!
Easy to read and follow
Well-structured & engaging content
Expert insights and opinions
Arguments were carefully researched and presented
On-point and relevant
Writing reflected the title & theme
Such an important topic. We talk to our kids all the time about finding a good balance between time on social media and real person to person interaction. Thank you for writing about this.
Hi Andrew! I've read this story and the one about spreading pandemic misinformation. They were both very well written but in my not-very-important opinion, read more like an article in a psychology magazine or textbook than for entertainment. If that was your intent, well done! I'm more of a story-with-a-moral-hidden-in-it kind of writer. Hope this was helpful and thanks for reading my story.


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These adorable Mini Stamped Wood Book Sets are perfect for styling tiered trays or adding a little something special to your home decor.
Each "book" is painted white and slightly distressed for a rustic farmhouse feel. Wording is hand stamped with vintage type font giving the book stack beautiful character.
These Mini Book Sets measure 3.5 in wide, 6.5 in long, and height varies depending on the number of books.
Because the books are made of wood, there may be slight imperfections like knots that might show through.
All Book sets come with twine wrapped around the stack and a greenery embellishment. Please leave a note if you want to add ribbon to your book stack.

domain: artistic


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|Publication number||US3427366 A|
|Publication date||Feb 11, 1969|
|Filing date||Mar 15, 1968|
|Priority date||Jun 18, 1965|
|Also published as||DE1620854A1, DE1620854B2, DE1645358A1, DE1694887A1, DE1694887B2, DE1694887C3, US3637558, US3714110|
|Publication number||US 3427366 A, US 3427366A, US-A-3427366, US3427366 A, US3427366A|
|Inventors||Joseph A Verdol, Patrick W Ryan|
|Original Assignee||Sinclair Research Inc|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (2), Referenced by (98), Classifications (42)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,427,366 HYDROCARBON RUBBER AND POLYURETHANE PREPARED FROM A POLYISOCYANATE AND AN HYDROXY TERMINATED DIENE POLYMER Joseph A. Verdol, Dalton, and Patrick W. Ryan, Chicago Heights, 111., assignors to Sinclair Research, Inc., New York, N.Y., a corporation of Delaware No Drawing. Continuation of application Ser. No. 536,292, Mar. 22, 1966. This application Mar. 15, 1968, Ser. No. 713,543 US. Cl. 260859 23 Claims Int. Cl. C08f 45/72, 27/10 ABSTRACT OF THE DISCLOSURE Rubber compositions containing hydrocarbon rubber and urethane resin which is the reaction product of a diisocyanate with an intermediate polyhydroxy polymer having an average of at least about 1.8 predominantly primary, terminal, allylic hydroxyl groups per average molecule and being an addition polymer of 075% by weight of an alpha-olefin monomer of 2 to 12 carbon atoms, and about 25 to 100% of a 1,3-diene hydrocarbon of 4 to about 12 carbon atoms, the intermediate polyhydroxy polymer having a viscosity at 30 C. of about 5-20,000 poises and a number average molecular weight of about 400-25,000. The urethane component is at least partially uncured when combined with the hydrocarbon rubber. These rubber compositions have improved tack and handling characteristics, improved resistance to attack by hydrocarbon oils and solvents as well as increased abrasion resistance and other desirable features, such as high tensile strength.
This invention is a continuation-in-part of copending application Ser. No. 465,161, filed June 18, 1965.
This application is a continuation of Ser. No. 536,292, filed Mar. 22, 1966, now abandoned.
The present invention is concerned with novel rubbers which have improved tack and handling characteristics. The compositions contain conventional hydrocarbon-type rubber and urethane rubber derived from particular hydroxy intermediate polymers. In accordance with the present invention, urethane elastomers derived from polydiene intermediate polymers having predominantly primary, terminal, allylic hydroxyl groups are combined with general purpose hydrocarbon-type elastomers such as natural rubber, styrenebutadiene rubber, cis-polybutadiene rubber, ethylenepropylene terpolymer rubber, butyl rubber and various other conventional elastomers. The combinations of these rubbers with urethane, according to this invention, show improved resistance to attack by hydrocarbon oils and solvents as well as increased abrasion resistance and other desirable features, such as high tensile strength.
It has been found that general purpose elastomers, especially ethylene-propylene rubbers, show increased tack when modified with urethane elastomers according to this invention. This is of important commercial significance, since one of the major shortcomings of commercially available ethylene-propylene terpolymer rubbers is their inherent lack of tack. Tack is a property of rubber which enables two fresh rubber surfaces to adhere or coalesce. For example, although the surfaces of rubbers may not appear tacky or adhere to foreign surfaces, the rubber surfaces adhere well to each other if the rubber possesses sufficient tack. Tack is very important from the practical standpoint, e.g., for producing rubber goods such as tires and other rubber articles. During the fabrication of rubber goods the surfaces should readily stick together so they may be rolled into place or molded. For example, plies and tread splices must hold during fabrication. =It is also desirable for rubber stocks to adhere well during milling on a rubber mill.
Urethane elastomers are known to have vastly different properties which distinguish them from the so-called general purpose or essentially hydrocarbon rubbers. Perhaps the most outstanding characteristics of urethane rubbers are their excellent abrasion resistance, high tensile strengths, and resistance to attack by hydrocarbon oils and organic solvents. However, urethane polymers known to the art generally are considered incompatible for blending with the conventional rubbers, which have a backbone structure composed largely of saturated or unsaturated hydrocarbon groups. The urethane resin which forms part of the composition of this invention is derived by isocyanate reaction with a diene intermediate polymer having a particular structure and containing allylic hydroxyl groups, which usually are at the ends of the main, that is, the longest, hydrocarbon chain of these usually liquid diene polymers. The intermediate polymers may, in general, have a viscosity at 30 C., of about 5-20,000 poises, preferably about 15 to 5000 poises. Ofter the intermediate polymer is obtained in a viscosity range of about 20 to 300 or 500 poises at 30 C. Preferably, the diene homopolymers have a viscosity of about 35 to 60 poises or about to 260 poises. Thus, the diene polymers are liquids or semi-solids flowable, at least when subjected to moderate pressure, at ambient temperatures or at temperatures upto about 400 F. The allylic hydroxyl-terminated intermediate polymers used in the present invention will have molecular weights in the range of about 400 to about 25,000 as determined by cryoscopic, ebullioscopic or osmometric methods. The preferred hydroxyl-containing diene polymers will be in the molecular weight range of about 900 to 10,000. In contrast, conventional diene polymers such as GR-S rubber are extremely high in molecular weight, e.g., in the range of several hundred thousand.
The hydroxy-terminated diene intermediate polymers employed to make the novel compositions of this invention differ from conventional diene polymers known to be telechelic and/ or hydroxy-containing in that the hydroxy components of the diene polymers used in this invention are in predominantly primary, terminal positions on the main hydrocarbon chain and allylic in configuration. Ordinarily, at least about 1.8 hydroxyl groups are present per molecule on the average and advantageously, there are at least 2.1 to say 3 or more hydroxyls per intermediate polymer molecule, preferably 2.1 to 2.8. As men'- tioned, the hydroxyl groups are predominantly allylic in structure, thereby being of a more reactive nature in the urethane-forming reaction and apparently providing an improved stability in the final elastomer product. The diene partial polymer has the majority of its unsaturation in the main hydrocarbon chain and this appears to provide polymers of improved elasticity characteristics.
The dienes which are employed to make the intermediate polymers are unsubstituted, Z-substituted or 2,3-disubstituted 1,3-dienes of up to about 12 carbon atoms. The diene preferably has up to 6 carbon atoms and the substituents in the 2- and/or 3-position may be hydrogen, alkyl, generally lower alkyl, e.g. of 1-4 carbon atoms, aryl (substituted or unsubstituted), halogen, nitro, nitrile, etc. Typical dienes which may be employed are 1,3-butadiene, isoprene, chloroprene, 2-cyano-1,3-butadiene, 2,3- dimethyl-1,3-butadiene, etc. The choice of diene will usually depend upon properties desired in the final elastomer, for example, chloroprene may be used, alone or in admixture with other dienes to produce oil-resistant and flame-proof rubbers. By allylic configuration is meant the alpha-allylic grouping of allylic alcohol, that is, the terminal hydroxyls of the first intermediate polymer are attached to a carbon adjacent to a double-bond carbon.
The number and location of the hydroxyl groups and the molecular weight of the intermediate polymer can be a function of polymerization temperature and the type of addition polymerization system employed in forming the polymer. It has been found that diene polymers of the desired configuration may be obtained using hydrogen peroxide as the catalyst for polymerization. This freeradical addition polymerization usually takes place at a temperature of about 100-200 0, preferably about 100- 150 C.
The reaction preferably takes place in a mutual solvent system; that is, one which dissolves both the diene monomer and the hydrogen peroxide. Suitable solvents are isopropanol, acetone, methanol, sec-butanol, n-butanol, npropanol and like alcohols having 2 to about 12 carbon atoms. The H O -solvent system is found to supply hydroxyl groups and the catalytic and solvent effects needed to produce the intermediate diene polymers of desired chemical and physical characteristics. In such a polymerization system, the alcohol serves as a solvent for the peroxide and as a solvent or diluent for the diene monomer and is used in an amount suitable to promote adequately rapid but controllable polymerization of the monomer material in the solution to form the diene polymers. The alcohol will be free of any group which would interfere with the production of the desired diene polymer. Saturated alcohols are preferred and often those having about the same carbon atom content as the diene monomer will be found most useful. Thus, propanol or isopropanol is often used in butadiene polymerization. The H o -alcohol system may also contain ketones, ethers, alcohol-ketones, alcohol-ethers and alcohol-esters which are miscible in water in all proportions and which do not contain polymerizable carbon-to-carbon unsaturation or otherwise interfere with polymerization or enter into the product. The peroxide material may be used in amounts of about 1% to 15% of the reaction mixture to assure a low molecular weight addition polymer product having more than two hydroxyl groups per molecule.
The usable intermediate polymers of butadiene will preferably conform to the following simplified chemical structure:
in which )2 plus p is greater than q, that is, the in-chain unsaturation accounts for more than 50% of the unsaturation. One or more of the hydrogens appearing in the above formula may be replaced by hy-droxyl in some of the molecules. This formula should not be understood as implying that the polymers are necessarily in blocks, but the cis-1,4-, trans-1,4- and vinyl (1,2) unsaturation are usually distributed throughout the polymer molecule. The letter It may represent a number suflicient to give a cis-1,4- unsaturation content of about 10-30 percent; p may be a number sufficient to give a trans-1,4-unsaturation content to the polymer in the range of about 40-70 percent while q may be sufficient to give a pendant 1,2-vinyl unsaturation of about 10-35 percent. Often the polymer will contain largely trans-1,4-units, e.g., about 50-65 percent and about 15-25 percent cis-1,4-units, with about 1525 percent 1,2-units. Branching may also occur in the above polymers, especially those prepared at higher temperatures.
Olefinically unsaturated monomers may be incorporated into the diene intermediate polymer products used in this invention and these may often be components which provide cross-linking sites. Usable monomers include alpha-mono olefinic materials of about 2 or 3 to 10 or 12 carbon atoms such as styrene, vinyl toluene, methyl methacrylate, methylacrylate, acrylic esters, vinyl chloride, vinylidene chloride, etc. Acrylonitrile, acrylic acid, vinylidene cyanide, acrylamide, etc., provide lowmolecular weight hydroxy-terminated diene intermediate copolymers which have sites suitable for cross-linking. As can be seen, the usable olefinic monomers may be ethylenes, substituted with halogen, aromatic hydrocarbon, or even cyano or carboxyl-containing radicals in some instances. The choice and amount of mono-olefinic monomer employed will often be determined on the basis of properties desired in the final elastomer resin. For example, solvent-resistant rubbers may be formulated by copolymerization of butadiene with acrylonitrile, or other mono-olefin, substituted with a non-hydrocarbon radical, to produce the intermediate polymer. Generally the amount of mono-olefinic monomer in the polymer will be about 0-75 by weight of the total addition polymer, preferably about 1 to 40% or even about 10-40%.
In addition to the homopolymers and copolymers comprised of single dienes and single mono-olefinic monomers, the present invention may also use polymers made from combinations of a plurality of dienes and mono-olefinic monomers. For example, mixtures of butadiene, isoprene and styrene can be polymerized to afford low molecular weight hydroxyl-containing interpolymers. Various combinations of dienes and mono-olefinic monomers may be copolymerized to produce hydroxyl-containing copolymers or interpolymers which may be used to form elastomers. Also, the polymer materials used in this invention may be given improved oxidation and ozone resistance by hydrogenating the hydroxyl-containing diene polymers to their corresponding more-saturated derivatives. Usually, the hydroxyl-containing diene polymers used in the present invention will at most be only partially hydrogenated, so as to provide a material which is more stable due to diminished unsaturation but which still has good elastomer properties.
The isocyanate material used to produce the urethane resin in the composition of this invention may be any one of a number of materials containing two or more isocyanate radicals. The usable agents for making the urethane polymers of this invention include aliphatic, including cycloaliphatic and aromatic diisocyanates such as 2,4-tolylene diisocyanate, metaphenylene diisocyanate, 2,6-tolylene diisocyanates (or mixtures of these materials), transvinylene diisocyanate, p,p'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, phenylene moieties. Typical reactions and reagents for such urethane amine-terminated products obtained from the reaction polymer production are illustrated below: dibasic acids with diamines; e.g., the reaction products POLYOLEFIN-POLYETHER-URETHANE RUBBER CH=CH2 POLYOLEFIN-POLYESTER-POLYETHER-UREHANE RUBBER Urethane resin formation to give the compositions of of dimerized unsaturated fatty acids with diamines. Dithis invention may also include diamine reactants to proamides of similar carbon atom range can also be emduce rubbers modified with urea-urethane resin. A wide ployed as reagents in the polymerization; e.g., materials variety of aromatic and aliphatic diamines may be emmade by the reaction of dibasic acids, acid chlorides or ployed as the reaction component to make such rub'ber anhydrides with ammonia. Other products which are usecompositions. These diamines may often be used in an ful are the reaction products of polyethers (e.g., poly[oxyamount sufficient to provide one amino group for each propylene] glycol and polytetramethylene glycol) and 0.1 to 9 hydroxyl groups, e.g., in the total of amino and ethylene imine; reaction products of hydroxyl-terminated hydroxyl groups, the amino group may represent about polyesters with ethylene imine are also useful as amine 10-90% of the total and hydroxyl groups may represent reactants for preparing urea-urethane resins according to about 90-10% of the total. The amino material may be this invention. Amine-terminated polybutadiene homofrom less than about 10 to 90% of the total of amino polymers and copolymers which have been made by the and hydroxyl material, but, of course, enough of the reaction of the allylic hydroxyl-terrninated polydiene hodiene intermediate polymer residue will be present to give mopolymers and copolymers with ethylene imine are also the desired physical properties. suitable as co-reactants in the production of rubber-urea- Typical amines of up to 40 or more carbon atoms which urethane compositions of the present invention. may be employed are aromatic diamines (both substituted The isocyanate is often employed in an amount sufand unsubstituted) such as 4,4'-methylene bis-(Z-chloroficient to supply about 0.1 to 10 isocyanate functional aniline)(MOCA), 3,3'-dichlorobenzidine (DCB), N,N'- groups per total active hydrogens of the diene interdisecondarybutyl p-phenylene diamine, N,N'-dibenzylmediate polymer and any other active hydrogenethylene diamine, menthane diamine, ethylene diamine, polyfunctional material used; the exact amount being subethanolamines, hydroxylamine, p,p' diphenylamine, pject to considerable variation within this range, depending, phenylene diamine, hexamethylene diamine, diethylene at least to some extent, on the manufacturing procedure triamine, tetraethylene pentamine, lauroguanamine and to be followed. Preferably, about 0.5 to 3 isocyanate diisocyanates, octamethylene, diisocyanate, 3,3 dimethoxy-4,4'-biphenyl diisocyanate and hexamethylene diisocyanate, as well as related aromatic and aliphatic isocyanates, which may also be substituted with other organic or inorganic groups that do not adversely affect the course of the reaction. These diisocyanates can be reacted with the diene intermediate polymers at ambient temperatures to form urethane linkages, apparently due to the increased reactivity given the hydroxyl groups by the allylic configuration. Such polymerization may require from a few minutes to 1 hour or to several days or weeks, depending upon, for instance, whether or not catalysts are employed in the reaction. Temperatures below ambient may also be employed. Elevated temperatures enhance cross-linking of the isocyanate-extended hydroxyl terminated diene polymers. Thus, after chainextending at ambient temperatures the temperature may be raised to up to about 200 C., preferably 100-150 C.; or both chain-extension and cross-linking may be obtained simultaneously at these higher temperatures. Thus, isocyanate reactions are generally conducted at temperatures of about 5 0-200 C.
011 C Hz Polyisocy-anates such as the materials sold commercially as PAPI (polyphenylmethane polyisocyanate) of the following structure:
CH=CH2 NCO NCO CH=CH2 CH: l 0 (13H; 0
Isocyanate terminated polyether It will be observed that the chain-extended polymer provides amino nitrogen having replaceable hydrogen which can be exploited in the cross-linking.
Rather than combine the polyisocyanate with only the alkyl-hydroxyl diene polymer, other polyfunctional reactants having at least two active hydrogens can be included with, before or subsequent to, combination of the polyisocyanate and alkyl-hydroxyl diene polymer. In other words the order of addition can be in any manner desired. Such other polyfunctional reactants may be up to about or more weight percent based on the total of its weight and that of the alkyl-hydroxyl diene polymer and when such other polyfunctional material is present it often is at least about 5 weight percent. Thus, other hydroxyl-containing materials may be incorporated with the allyl-hydroxyl diene polymer fed to the reaction. For example, a hydroxyl-containing intermediate polybutadiene may be mixed with materials such as polypropylene glycol, polyethylene glycol, interpolymers of polyethylene and polypropylene oxides, and bydroxy-terminated polyesters which are normally employed to make conventional urethane rubber. In such cases polymers are formed which have polybutadiene moieties linked through chain-extension at the hydroxy residues to glycol, polyolefin, polyether or polyester groups are supplied for each diene polymer hydroxyl or other active hydrogen and the proportions often approach one mole of diisocyanate per mole of other polyfunctional material. Advantageously, about 410% tolylene diisocyanate can be employed in urethane formation, preferably about 5-8% based on the total weight of the polydiene employed, especially when no other active hydrogen material is present of markedly different molecular weight. Preferably, in a urea-urethane polymer, there will be about 1 to 1.5 isocyanate residues for each moiety reactant with the isocyanate, that is, the isocyanate residues will equal or surpass the total of hydroxyl and amino residues.
Resin formation may take place in a single step by blending in the individual ingredients, diisocyanate on the one hand, and diene intermediate polymer, with or without another polyfunctional, e.g., glycolic and/or diamino material, on the other hand.
Two-step procedures may also be employed in forming the novel compositions of this invention. In such procedures, an excess of the diisocyanate may be reacted with one or two of the other components, e.g., the diene intermediate polymer, the conventional glycol and/or the diamine, to produce a diisocyanate terminated prepolymer, which may subsequently be reacted with the remaining one or two of the above-mentioned other components to give the final urethane or urea-urethane resin. Preferably, the prepolymer is a diisocyanate terminated derivative of the polydiene intermediate polymer.
The procedure employed in combining the conventional or hydrocarbon type elastomer with the urethane resin is subject to a number of alternatives. For example, the hydroxyl-terminated polydiene resin may be milled or admixed with the general purpose or hydrocarbon type elastomer and the isocyanate reactant subsequently milled into the system. Or the isocyanate reactant may be initially milled or admixed with the general purpose elastomer, followed by the addition of the hydroxylterminated resin. Other polyfunctional reactants can be added with any component desired or can be separately added to the blends. These mixtures, regardless of the sequence of addition of the hydroxyl-terminated resin and other reactants, contains, at least upon initial mixing, the urethane component in an unreacted, uncured or partially cured state, i.e., is at least partially uncured, Within the general purpose elastomer system. Thus, the urethane component must not be completely cured before admixture with the hydrocarbon-type rubber. This lack of cure when mixing must be suflicient to provide compatible materials and the presence of either unreacted isocyanate or unreacted hydroxyl groups is indicative of the uncured urethane state. Although it is preferred that the mixture of urethane and hydrocarbon type rubbers becomes eventually more or less completely cured, this may not be necessary in some instances, especially when the hydroxyl component is in sufficient excess. Thus, in Examples I-IV below, the isocyanate-to-hydroxyl ratio was sufiiciently low that the mixture, which had been cured for a period of time, was still in a partially urethane cured state due to the presence of unreacted hydroxyl groups. The urethane material was millable with the ethylene-propylene rubber and there was no necessity for the use of a final urethane curing treatment.
The general purpose elastomer may be heated, e.g., in a Banbury mixer or rubber mill to about TOO-250 F. prior to addition of the urethane or urethane-forming reactants. The preferred method for incorporating the urethane into the general purpose elastomer is to pre-mix the polydiene hydroxyl intermediate polymer with the diisocyanate reactant. While the mix is in a partially cured state (liquid, solid or semi-solid) it is blended into the general-purpose elastomer as on a rubber mill or Banbury-type mixer. The urethane reaction or cure may be completed in the general purpose elastomer, apparently to afford a solid solution of urethane rubber in the general purpose rubber. This mixture can then be compounded and cured using conventional sulfur or peroxide curing agents, if desired, Which serves to interlink or co-cure the urethane and general purpose rubber.
Also, the hydroxyl-terminated resin may be mixed with the diisocyanate reactant and cured at ambient or elevated temperatures to a millable gum. This gum may then be milled into the general purpose elastomer. The millability of the urethane elastomers is dependent often upon the ratio of isocyanate to liquid diene resin employed for the formation of the urethane elastomer. For example, when the NCO/OH ratio (molar ratio) of isocyanate and polydiene reactant is low, e.g., about 0.6 or below, the elastomer produced therefrom is often tacky, even When cured over a substantial period of time and, therefore, is readily incorporated into the general purpose elastomer merely by milling at ambient temperatures or by mixing in a Banbury mixer with the general purpose elastomer. When the ratio of NCO/OH (molar ratio) in the reactant mixture is above about 0.6, such as near unity, e.g., 0.9 to about 1.2, the products are preferably cured to a lesser extent prior to milling with the general purpose elastomer. If complete curing of these systems is carried out, the blending operation is difiicult, since the urethane elastomer system possesses a tight, wholly or partially cross-linked network which is diflicult to mill or mix on a Banbury mill with the general purpose elastomer.
The cross-linking of proximate chains of the polymer may be brought about through the polydiene residues, the chain-extending agent residues, or both. The use of the preferred polydiene materials having at least 2.1 hydroxyls per molecule, allows cross-linking by means of urethane linkages when a suitable amount of diisocyanate is employed in the reaction. Also, the crosslinking may, and usually does, occur between the urethane moieties themselves of adjacent polymer molecules. After the urethane reaction, a post-cure using gamma rays, or a treatment similar to conventional vulcanization may be performed. Such a procedure generally employs the same conditions and reagents as employed with conventional rubber compositions. Sulfur, used as sulfur, thiuram derivatives and other materials commonly employed to vulcanize natural rubber, GRS rubber and related synthetic polyolefin rubbers, may thus be added to promote cross-linking. Generally, amounts of vulcanizing agents common to the art can be herein employed, for instance, about 1-50 parts, preferably about 1-10 parts by weight per part of polymer, as well as conventional vulcanization temperatures.
The isocyanate-terminated polymer described above also may be admixed with the general purpose elastomer using a rubber mill, Banbury mixer or other conventional mixing equipment. After the prepolymer is admixed with the general purpose elastomer, a diol (such as Z-ethylhexane diol) or other suitable polyol described above may be mixed into the mixture on a rubber mill or Banbury mixer. The final blend can then be cured at ambient temperature or elevated temperature to form a blend of high molecular weight linear or cross-linked elastomer within the general purpose elastomer network. The final blend may then be formulated with sulfur, zinc oxide, stearic acid and conventional rubber curing aids and accelerators to afford an elastomeric product showing improved tensile properties, abrasion resistance, resistance to swelling by organic solvents and oils. In place of, or along with, the diol, a diamine such as 3,3'-dichlorobenzidi.ne, 4,4'-'methylene-bis-2-chlonoaniline, lauroguanamine, etc., may also be employed to chain extend or cross-link the prepolymer and provide a urea-urethane resin, with the mole ratio of isocyanate to amine plus polyol reactant being maintained near unity, e.g., the mole ratio of NCO/ OH plus NH is preferably maintained about 0.9 to 1.1.
Urea-urethane resin formation may take place in a single step by blending the individual ingredients, diisocyanate on the one hand, and diene intermediate polymer with or without diamino materials and/or glycolic materials on the other hand, in about stoichiometric proportions, with the natural or other conventional rubber to be improved according to this invention. The urea-urethane products are blended into the general purpose elastomers prior to efiecting complete urethane-type cure of the ureaurethane products. The resulting blend can then be cured at elevated temperature and later formulated with conventional rubber curing aids as described. The final formulation can then be heat-cured at elevated temperature. Thus, the hydroxyl-terminated diene resin may be admixed with the diamine reactant and degassed in vacuo. The isocyanate reactant can then be added and the mixture becomes fluid or paste-like in consistency. The liquid or paste can then be admixed with the general purpose elastomer on a rubber mill or Banbury mixer. The finished blend is then cured at ambient or elevated temperature, usually followed by a conventional sulfur or peroxide cure.
Alternatively, after the hydroxyl-terminated diene resin is admixed with the diamine reactant and degassed in vacuo, the mixture may be blended with the general pur- 1 pose elastomer on a rubber mill, Banbury mixer or other suitable equipment. The isocyanate reactant can then be added using the same mixing equipment. The resulting blend may be cured at ambient or elevated temperatures, followed by final sulfur or peroxide curing. In still another mode of operation, the hydroxyl-terminated diene resin may be admixed with the general purpose elastomer on a rubber mill, Banbury mixer or other mixer. The diamine reactant(s) and isocyanate reactant(s) are then added, either component being added first. The resulting blend is then post-cured at ambient or elevated temperature, followed by conventional sulfur or peroxide curing. Of course, many other alternate methods may be employed so long as the desired end-result is obtained.
Alternatively, the general purpose elastomers may be modified with the two-step or prepolymer urethane elastomers by first admixing the liquid prepolymer with the diol, polyol or amine reactant. This mixture is then blended into the general purpose elastomer using a rubber mill, Banbury mixer or other conventional mixing equipment. The blend is then post-cured at ambient or elevated temperature to form a linear or cross-linked polyurethane network within the general purpose elastomer. The final blend can then be formulated with sulfur, etc., as described above, and cured at elevated temperature to afford a final product showing improved tensile properties, abrasion resistance, resistance to swelling by organic solvents and oils. It should be pointed out that the modified general purpose elastomers prepared by blending with the prepolymer urethane elastomers of this invention show improved tack prior to carrying out the final sulfur cure; therefore, there is an improvement in the ease with which rubber goods may be fabricated.
Conventional urethane catalysts such as stannous octoate, diazobicyclooctane (DABCO), dibutyl tin dilaurate, lead naphthenate, cobalt naphthenate and the like may be employed to catalyze the formation of the urethane elastomer within the general purpose elastomer network. The catalyst concentrations may often vary from about 0.03 to about 1 part per hundred parts of hydroxyl-terminated diene polymer/urethane elastomer system which is added to the general purpose elastomer.
As mentioned previously, the hydrocarbon-type rubber with which the urethane of this invention is to be blended is selected from known single-and-multiple-component elastomers. Useable rubbers include natural rubber, styrene-butadiene and related type terpolymer rubbers, butyl and cis-polybutadiene rubber. This invention, as also mentioned, affords significant improvement to ethylenepropylene rubbers. Such rubbers are of important com- 12 mercial potential because the monomers from which they are made are significantly less expensive than diolefin monomers. Copolymers of ethylene and propylene generally display elastomeric properties over a wide range of compositions, roughly 25-75% of each component, and have the properties of unvulcanized elastomers when the molecular weight is sufficiently high. These materials are generally soluble in hydrocarbon solvents at room temperature, have a relatively low modulus of elasticity, high resilience and considerable creep under prolonged stress. Such polymers may be prepared with a susceptibility for vulcanization or other cross-linking by including small amounts of alpha-olefins or other copolymerizable materials which retain a reactive group after the polymerization. Diolefins such as dicyclopentadiene, cyclooctadiene, Z-methyl, 1,4-pentadiene, etc., are often the preferred materials in such situations. The vulcanized EP terpolymers show good resistance to aging and have greater tensile strength than natural rubber or GR-S polymers. Many E-P terpolymers contain about 35 to mole percent ethylene, about 15 to 60 mole percent propylene and about 1 to 5 mole percent diene. Preferably, the amounts are about 50 to 67 mole percent ethylene and about 23 to 50 mole percent propylene, based on their total. Ethylene-propylene copolymers can be prepared by free-radical additional polymerization techniques. Such catalysts as the Ziegler type (usually mixtures of TiCL, or similar compounds with trialkyl aluminum compounds), supported transitional metal oxides, such as chromium oxide on a silica/ alumina support or M00 supported on alumina and activated by partial reduction with hydrogen may be employed. Generally such polymerization reactions are carried out under low pressure operating conditions.
The urethane rubber employed in this invention may be miscible in all proportions with conventional hydrocarbon-type rubbers. Thus, the composition of this invention may contain as little urethane rubber or as little conventional rubber as is needed to have a significant effect in the application desired, say, as little as 1% of each rubber. More usually, the finished composition of this invention may contain about 1100% urethane resin, based on the weight of the hydrocarbon-type rubber. Often, about 4-50% urethane rubber, advantageously about 10-30% is employed.
Along with urethane resin and conventional hydrocar hon-type rubbers, the novel compositions of this invention may contain bulk extenders such as extender mineral oils (including asphalt and similar heavy hydrocarbons), strengtheners, such as carbon black, and pigments, fillers, etc., as commonly used with general purpose rubbers. Ordinarily these ingredients may form a considerable proportion of the final product, being as little, for example, as 1% or less of the total rubber ingredients up to ten times or more of such ingredients. Extender oil and carbon black components equalling the weight of the general purpose and urethane rubber combined is not unusual. The extender oils, carbon black, etc., may be incorporated into the general purpose hydrocarbon-type rubber before the urethane resin or its ingredients are added to the mixer or mill; alternatively, after incorporation of the urethane elastomer into the general purpose elastomer, the resulting product is further blended with sulfur, zinc oxide, stearic acid, inert or reinforcing filler, extender oils and resins, etc., and the final mixture cured at elevated temperatures of say about 200-400 F., preferably about 275-325" F. Peroxide cures may also be effected at about the same temperature ranges.
The following examples of compositions according to this invention illustrate this invention, but should not be considered limiting.
EXAMPLE I Polybutadiene No. 45 is a polybutadiene homopolymer having a viscosity of 50 poises at 30 C., a hydroxyl content of 0.95 meq./gm., a hydroxyl number (mg.
KOH/ gm.) of 53, and average molecular weight of 2200- 2500, about 2.1-2.2 terminal, allylic, hydroxyl groups which are predominantly primary per polymer molecule, and an iodine number of 398. It can be prepared by polymerizing 100 parts of butadiene in the presence of 70 parts of isopropanol and 10 parts of hydrogen peroxide in an aluminum clad autoclave at 118 C., 'for 2 hours.
94.5 parts of this homopolymer was reacted with 5.5 parts of tolylene diisocyanate (a commercial mixture of 80% 2,4-TDI and 20% 2,6-TDI) and the mixture allowed to cure for one week at room temperature. 25 grams of this urethane was placed on a roller mill at 120 C., along with a like quantity of a commercially obtained ethylene-propylene terpolymer rubber obtained from the Naugatuck Chemical Co. The materials were comilled for several minutes. At the end of this time the mixture appeared to be homogeneous. To the mix on the roller mill was added one gram of sulfur, 2.5 grams of zinc oxide, -1 gram of stearic acid and 1 gram of tetramethyl thiuram disulfide. Milling was continued for about 15 minutes and the rolled sheet was cured in a molding press at about 150 C. at several hundred pounds pressure. As far as could be determined, covulcanization had taken place to give elastomeric materials containing urethane as well as ethylene-propylene rubber characteristics.
EXAMPLE II Runs were conducted similar to Example I except that the urethane elastomer was comilled with natural rubber and with Hycar, a commercially obtained nitrile rubber comprising a copolymer of acrylonitrile and butadiene. These blends were translucent after milling and oil extension.
EXAMPLE III EXAMPLE IV The run of Example III was repeated using a urethane system prepared from 90 parts of the polybutadiene homopolymer and 10 parts of a polypropylene glycol (2025 molecular weight) and 7.2 parts of tolylene diisocyanate. The mixture was cured at 65 C. for 64 hours. The resulting urethane gumstock was milled with natural rubber in equal quantities to produce a soft gumstock which was sulfur curable, oil extendible and readily reinforced with carbon black.
EXAMPLES V T O VII A polybutadiene homopolymer was prepared by polymerization of 100 parts of butadiene with 70 parts of isopropanol and 12 parts of hydrogen peroxide (50%) at 118 C., for 2.5 hours. The homopolymer had the following properties:
H Content 0.88 meq./g. I. R. Analysis Trans 59.2. Mol. Wt. Osmometric 2,350 Vinyl 19.8.
Mol. Wt. End Group Analysis 2, 270
It was estimated that the polymer contained an average of about 2.1 hydroxyl groups per molecule.
200 grams of this polydiene polymer were mixed with 15.2 grams of tolylene diisocyanate (NCO/OH=1.0). During the hour after the mixture, a gram portion, a 25 gram portion and a gram portion of this mixture were added to samples of natural rubber amounting to 95,
and grams respectively. Each rubber sample was being milled on a 2 inch rubber mill heated to 240 F. (20 p.s.i. steam pressure). Each polymer mixture sample was added over a five minute period and allowed to comill for an additional 15-20 minutes. The urethane rubber mixtures were removed from the mill and cured in aluminum molds at 100 C., for 4 hours. The samples were allowed to further cure at room temperature for two weeks before taking test specimens.
The remainder of the gumstocks, after test specimens were taken, were remilled on the rubber mill. It was found that after curing the urethane in the natural rubber matrix the raw gumstocks had better processability characteristics. The urethane modified rubber was easier to mill and had considerably more tack than unmodified natural rubber. Using a conventional rubber recipe, vulcanization ingredients were added to the urethane-modified rubbers on the rubber mill, and subsequently, cured at 300 F. The vulcanized urethane modified natural rubbers showed increased abrasion resistance, increased solvent resistance and, in general, better physical properties than natural rubber vulcanizate.
EXAMPLE VIII A polybutadiene copolymer was prepared as above but with 15% acrylonitrile substituted for a like amount of butadiene. The resulting liquid intermediate polymer had a hydroxyl equivalent of 0.71 meq./g., and was estimated to contain 2.5 average hydroxyl groups per molecule. To 100 grams of this polymer 2 grams of 3,3'-dichlorobenzidine, 3 grams of Ethyl 702 antioxidant and 1.0 gram of dibutyl tin dilaurate were added, mixed at 140 C., and degassed for 1 hour.
To grams of a commercially obtained styrenebutadiene rubber on a two-inch rubber mill at 240 F., was added 5 g. of the above mix to which 0.6 g. of tolylene diisocyanate had just been added. The addition of the urea-urethane mix took 20 minutes and comilling was allowed for an additional 10 minutes. The gumstock was removed from the mill and the urea-urethane modified rubber was allowed to cure 4 hours at C., and two weeks at room temperature. After obtaining test specimens, the remaining urea-urethane modified rubber was remilled and conventional vulcanization ingredients added on the rubber mill. The urea-urethane modified rubber was then vulcanized at 300 F., for thirty minutes and a urea-urethane natural rubber covulcanizate was obtained.
EXAMPLE IX A prepolymer containing 9% free NCO was prepared by reacting the hydroxyl-terminated polybutadiene intermediate polymer of Example V, with excess tolylene diisocyanate at 60-80 C., for two hours. To 90 g. of commercially obtained styrene-butadiene rubber on a 2" rubber mill at 240 F., was added 8 g. of the prepolymer and 2.5 g. of 1,3-ethylhexane diol which had been mixed just prior to addition to the rubber. The milling time was 20 minutes and the mixture was allowed to comill for an additional 10 minutes. The urethane modified rubber was cured at 100 C., for 4 hours and two weeks at ambient temperature. After obtaining test specimens the urethane modified rubber was covulcanized using a conventional rubber recipe.
EXAMPLE X In the same manner as above Tenamene-4(N,N'-bis- [1,4-dimethylpentyl]-p-phenylene diamine) was used in place of 1,3-ethylhexandiol as achain extender to yield a urea-urethane modified covulcanized rubber.
EXAMPLES XI-XLIII Using the above procedure the urethane and ureaurethane modified rubbers described in Table I, below, were prepared. In this table Type A urethane is an intermediate hydroxyl-terminated polybutadiene mixed with tolylene diisocyanate as in Examples I-III; Type B is a liquid hydroxyl-terminated butadiene-acrylonitrile copolymer, as in Example 1V, mixed with 6.2 grams, per 100 grams of intermediate polymer, of tolylene diisocyanate. Type C urethane is a styrene-butadiene copolymer liquid containing about 25% styrene and having a hydroxyl equivalent of 0.75 meqJg. and about 2.1 average hydroxyl groups per molecule, estimated. It was made by the method of Example I and mixed with 6.5 grams tolylene diisocyanate for each 100 grams intermediate polymer. Types D, E and F are urea-urethanes prepared from 200 grams of hydroxyl-terminated diene polymer, 22.3 grams of Curithane C-126 diamine, 2 grams Ethyl 702 anti-oxidant and 0.67 gram dibutyl tin dilaurate catalyst. In Type D, the polybutadiene prepolymer of Type A is employed; in Type E, the liquid polybutadienestyrene copolymer of Type C was employed; in Type F, the prepolymer is the acrylonit-rile copolymer of Example IV. Each of types D, E and F comprised a mixture of 0.7 gram tolylene diisocyanate to each grams of urea-urethane.
TABLE I 5. The composition of claim 4 in which the diene is butadiene.
6. The composition of claim 1 in which the hydrocarbon rubber is ethylene-propylene terpolymer rubber containing about to 75% propylene.
7. A composition consisting essentially of hydrocarbon rubber and about 1-l00% by weight of the rubber, of urea-urethane resin made by reaction of a diisocyanate, a diamine and an intermediate polyhydroxy polymer having an average of at least 2.1 predominantly primary, terminal, allylic hydroxyl groups per molecule and being an addition polymer of 0-75% by weight of an alphaolefin monomer of 2 to 12 carbon atoms, and about 25-100% of a 1,3-diene hydrocarbon of 4 to about 12 carbon atoms, said intermediate polymer having a viscosity at C., of about 520,000 poises and a number average molecular weight of about 40025,000, said urethane being at least partially uncured when combined with said hydrocarbon rubber.
8. The composition of claim 7 in which the diene is butadiene.
9. The composition of claim 7 in which the urea- Urethane Polymer Rubber Comilling Rubber (parts) Milling Time (min) Type (parts) TDI (pts.) Time (min.)
XI Natural, 95 D-5 5 15 XII-.- Natural, 75... 13-22 30 15 XIIL- Natural, 90 D-9 10 15 XIV Styrene-butadiene, 75. D-22 30 15 XV. Styrene-butadiene, D44 1 5 XVI- Styrene-butadiene, 95- D-5 5 15 XVII. Styrene-butadiene, 90- D-Q 1 5 15 XVIII Styrene-butadiene, 95- A-5 10 10 IX-. Styrene-butadiene, 90- A-lO 20 10 XX-.. Styrene-butadiene., 75. A-25 4O 10 13-5 10 10 B-10 15 10 B-25 30 10 13-24 30 10 13-5 30 10 B-5 30 10 C5 10 10 C-10 15 10 C-25 30 10 (3-25 30 10 F-5 0. 6 10 10 F-Q 1. 1 20 10 XXXIII... Natural, 75 F23. 5 2. 6 25 5 XXXIV.-- Styrene-butadiene, 95-.. F-5 0. 6 20 10 XXXV.. Styreue-butadiene, 90. F-9 1. 1 25 7 XXXVI. Styrene-butadiene., 75. F-22. 5 2. 5 15 XXXVIL. Ethylene-propylene, 95 F-5 0.6 15 10 XXXVIII, Natural, 95 E4. 5 0. 5 8 12 XXX Natural, 90... E-Q. 0 1. 1 10 10 L Natur 13-224 2.6 16 9 XLI-. Styrene-butadiene, 95... EA. 5 0. 5 8 12 XLII. Styrene-butadiene, EH). 0 1. 1 9 11 XLIII Styrene-butadiene. 75- E-22. 4 2. 6 18 7 It is claimed:
1. A composition consisting essentially of hydrocarbon rubber and urethane made by reaction of a diisocyanate with an intermediate polyhydroxy polymer having an average of at least about 1.8 predominantly primary, terminal, allylic hydroxyl groups per average molecule and being an addition polymer of 075% by weight of an alpha-olefin monomer of 2 to 12 carbon atoms, and about 25 to of a 1,3-diene hydrocarbon of 4 to about 12 carbon atoms, said intermediate polymer having a viscosity at 30 C., of about 520,000 poises and a number average molecular weight of about 40025,000, said urethane being at least partially uncured when combined with said hydrocarbon rubber.
2. The composition of claim 1 in which the intermediate polyhydroxy polymer has an average of about 2.1 to 2.8 predominantly primary, terminal, allylic hydroxyl groups per average molecule.
3. The composition of claim 2 in which the diene is butadiene.
4. The composition of claim 2 in which the urethane resin comprises about 10 to 30% by weight of the composition.
urethane resin comprises about 10-30% by weight of the composition.
10. A method for making a blend of urethane resin and hydrocarbon rubber which consists essentially of partially reacting a diisocyanate with an intermediate polyhydroxy polymer having an average of at least about 1.8 predominantly primary, terminal, allylic hydroxyl groups per average polymer molecule and being an addition polymer of 075% by weight of an alpha-olefin monomer of 2 to 12 carbon atoms, and about 25-100% of a 1,3-diene hydrocarbon of 4 to about 12 carbon atoms, said intermediate polymer having a viscosity at 30 C., of about 520,000 poises and a number average molecular weight of about 40025,000, blending said partially reacted product with hydrocarbon rubber andv vulcanizing the blended product.
11. The composition of claim 1 in which the intermediate polyhydroxy polymer has the majority of its unsaturation in the main carbon chain, and said urethane is present in amount of about 4 to 50% by weight.
12. The composition of claim 1 in which the intermediate polyhydroxy polymer has a cis-1,4-unsaturation content of about 1030 percent, a trans-1,4-unsaturation 17 content of about 40-70 percent and a pendant 1,2-vinyl unsaturation of about -35 percent.
13. The composition of claim 12 in which the hydrocarbon rubber is ethylene-propylene terpolymer rubber containing about 25 to 75% propylene.
14. The composition of claim 12 in which the intermediate polyhydroxy polymer is obtained by addition polymerization of said alpha-olefin monomer and said 1,3- diene hydrocarbon in solution in a saturated alcohol of 2 to 12 carbon atoms containing hydrogen peroxide dissolved therein.
15. The composition of claim 12 in which the intermediate polyhydroxy polymer is obtained by addition polymerization of butadiene in solution in an alcohol containing hydrogen peroxide dissolved therein, said alcohol being selected from the group consisting of propanol and isopropanol.
16. The composition of claim 7 in which the intermediate polyhydroxy polymer has the majority of its unsaturation in the main carbon chain.
17. The composition of claim 7 in which the intermediate polyhydroxy polymer has a cis-1,4-unsaturation content of about 10-30 percent, a trans-1,4-unsaturation content of about 40-70 percent and a pendant 1,2-vinyl unsaturation of about 10-35 percent.
18. The composition of claim 7 in which the intermediate polyhydroxy polymer is obtained by addition polymerization of said alpha-olefin monomer and said 1,3- diene hydrocarbon in solution in a saturated alcohol of 2 to 12 carbon atoms containing hydrogen peroxide dissolved therein.
19. The composition of claim 7 in which the intermediate polyhydroxy polymer is obtained by addition polymerization of butadiene in solution in an alcohol con- 18 taining hydrogen peroxide dissolved therein, said alcohol being selected from the group consisting of propanol and isopropanol.
20. The method of claim 10 in which the intermediate polyhydroxy polymer has the majority of its unsaturation in the main carbon chain.
21. The method of claim 10 in which the intermediate polyhydroxy polymer has a cis-1,4-unsaturation content of about 1030 percent, a trans-1,4-unsaturation content of about -70 percent and a pendant 1,2-vinyl unsaturation of about 10-35 percent.
22. The method of claim 10 in which the intermediate polyhydroxy polymer is obtained by addition polymerization of said alpha-olefin monomer and said 1,3-diene hydrocarbon in solution in a saturated alcohol of 2 to 12 carbon atoms containing hydrogen peroxide dissolved therein.
23. The method of claim 10 in which the intermediate polyhydroxy polymer is obtained by addition polymerization of butadiene in solution in an alcohol containing hydrogen peroxide dissolved therein, said alcohol being selected from the group consisting of propanol and isopropanol.
References Cited UNITED STATES PATENTS 3/1965 Hsieh 260-859 8/1967 Mastin 260859 SAMUEL H. BLECH, Primary Examiner.
P. LIEBERMAN, Assistant Examiner.
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|Cooperative Classification||C08L75/04, C08G18/69, C08G18/87, C08L75/14, C08L95/00, C08L2555/24, C08K5/01, C08L53/02, C08C19/38, C08L9/00, Y10S528/905, A61F5/44, Y10S528/906, C08L2555/80, C08L21/00|
|European Classification||C08L75/04, C08L75/14, C08L21/00, C08K5/01, C08L9/00, C08L95/00, C08G18/69, C08C19/38, C08G18/87, A61F5/44|

domain: chemistry


text: With all the ongoing waterfront development, Brooklyn emerges as a hub for bespoke furniture makers. They often use high quality, exotic materials sourced locally from demolished industrial buildings. Old-growth wooden beams and floorboards. Redwood from water towers. Even this highly durable and fire resistant Brazilian walnut (ipe) salvaged from the Coney Island boardwalk. The supply of this lumber makes it profitable for makers to upcycle furniture Made in Brooklyn.


The Beatles' eighth album, Sgt. Pepper’s Lonely Hearts Club Band, first hit the record stores in June 1967. The album was created at Abbey Road Studios and features classics like “Lucy In The Sky With Diamonds” and “With A Little Help From My Friends” in addition to the title track. Fifty years later, Sgt. Pepper remains a fan favorite, and is being re-issued with new mixes and tracks. Today on Google Earth’s storytelling platform, Voyager, we’re celebrating not only this beloved, influential album, but the whole of the Fab Four’s monumental contributions to rock ‘n’ roll.
The global Voyager tour highlights significant moments and places in The Beatles’ career. Their journey starts at Liverpool’s iconic Cavern Club, and ends at Strawberry Fields in New York’s Central Park, where a black-and-white tiled memorial honors the life of John Lennon. You can also fly to the Hamburg nightclub where the band performed almost nonstop for 48 days; the New York theater where they made their historic first live TV appearance in America; and India, where they experienced spiritual awakenings in the Maharishi’s ashram.
Join the Fab Four as they tour the globe with Google Earth’s Voyager.Header image courtesy of Local Guide Austin Ayodeji


text:
Escape Game Cartoon Village
Telecharger escape game cartoon village fichier online vostfr francais
escapegame#firstescapegames#feg Play free online escape games. Cartoon Village Escape Walkthrough : FirstEscapeGames - FEG Escape Game: Cartoon Village Escape is . Escape Game: Cartoon Village Walkthrough, Hints, Tips, Cheats, Solution, Help, Guide, Tricks, Answers. Escape Game: Cartoon Village is another point and click escape game. There is a farmer living in the cartoon village. Today, he got trapped in a cottage and he . Escape Game: Cartoon Village is another point and click escape game. There is a farmer living in the cartoon village. Today, he got trapped in a cottage and he . Read reviews, compare customer ratings, see screenshots, and learn more about Escape Game Cartoon Village. Download Escape Game . Download Escape Game - Cartoon Village apk 1.0.7 for Android. Help the farmer escape from the cottage with your puzzle solving skills. Escape Game Cartoon Village FirstEscapeGames. 1 Étoile. 2 Étoiles. 3 Étoiles. 4 Étoiles. 5 Étoiles. (4 notes, moyenne de: 2,75 sur 5). Loading. Escape Game Cartoon Village is an escape game developed by First Escape Games.
The velvet express. La belle et la bete dessin anime avi. Probleme de la page twitter sur c. Jonah hex 720p. Carte e gps mio digi walker c220. Pokemon serie soleil et lune ultra aventure. Whatsapp v2.19.134. Restaurez votre 2cv pdf. Fiche technique robinet plonge inox. Banzai le film.

domain: entertainment


This is Section 5’s weakness, and in 2009, Roberts essentially told Congress to go fix it. By a vote of 8-1, the Supreme Court let Section 5 stand, but “current burdens,” Roberts wrote, “must be justified by current needs.” He has a point: Why does the Justice Department have the power to block voter ID laws in Texas and South Carolina, but not in Pennsylvania, Missouri, and Wisconsin? Shouldn’t Congress figure out what protections the right to vote merits, and then enforce them everywhere? Protecting the right to vote only against racially discriminatory measures, as opposed to all unjustifiable restrictions on voting, might no longer be the smartest approach, even for minority voters. As Pildes puts it, “If we were creating the law for the first time now, you wouldn’t pass Section 5. It's not clear we would pass a law structured along the unique lines of Section 5. We might well pass a law that protected the voting rights of all citizens uniformly.”
But before you decide it’s OK for the Supreme Court to scrap Section 5, think about how likely it is that Congress is going to pass a New and Improved Voting Rights Act any time soon. And think too about all those voter ID requirements, and efforts to curtail early voting, that states have tried in the last couple of years. They are the contemporary version of voter suppression for poor and minority voters, who tend to vote Democratic—a throwback and a scourge. We need every weapon at our disposal to beat them back. It’s true that laws restricting voting have so far mostly been put on hold or struck down—the Brennan Center counts 11 court decisions blunting their impact, and two repeals. Courts turned to a variety of legal theories, from state constitutions to Bush v. Gore. Section 5 wasn’t the only remedy, but it’s what stopped the voter ID laws in South Carolina and Texas, and early-voting restrictions in Florida.* Section 2, by contrast, didn’t come into play. So we really don’t know if that part of the law can do the job Section 5 is currently doing.
Just as important, the minority vote would have led to a very different story if the 2012 results had been just a few points more in favor of Republican candidate Mitt Romney. If voter ID laws had succeeded in suppressing turnout among blacks and Hispanics, we’d see this election in a wholly different, and alarming, light.
That’s what I mean about timing: The Supreme Court should not be in the business of telling Congress it can’t pass a civil rights law based on the outcome of the last two presidential elections. Not in light of the decades of dismaying history that came before. Section 5 isn’t perfect, but it’s what we’ve got.
Before the Supreme Court decides the Alabama case, I want to learn a lot more about how the Voting Rights Act is actually playing out on the ground. For example, the law also addresses redistricting, which means that it provides some check to gerrymandering. How is that actually working in Southern states, and to whose benefit? And what kind of voter suppression has Section 5 headed off recently? I’m going to dig into those questions by looking at some of the current cases the Justice Department has addressed. If you have experiences to share or tips about what I should investigate, I’d love to hear them—send to firstname.lastname@example.org. Email may be quoted in Slate unless you stipulate otherwise. If you want to be quoted anonymously, please let me know.


AboutShaw Speed & Custom
Shaw Speed & Custom, part of the Shaw Harley-Davidson dealership, is based in the South of England just outside of Brighton. Shaw's is not your average Harley-Davidson Dealership; now in its 14th year, the team has won the prestigious Bar and Shield 6 times, an award given for customer service and excellence.
The Speed and custom wing continues these high standards of excellence and has collected bike show awards in Europe and the US. One of the shop's finest achievements was taking 1st place in the Modified Harley-Davidson class at Sturgis AMD World Championship of Bike Building, a feat no other global dealer has achieved.
Dealer Principal of Shaw Harley-Davidson, Steven C. Willis, is also the Team Principal for Shaw Speed & Custom. He has been with the dealership since it was opened in 2002. Steven’s passion for the custom shop comes from working with a world-class team and creating unique and striking bikes for his clients.
Being World Champions motivates the team to continually push what is possible, and always produce the best bikes for our customers. Every bike we build must fit our three core objectives: attention to detail, rideability and, most importantly, that it blends with its owner.
The Speed shop is situated above our technical department and therefore every bike is built under the watchful eye of our Team Principal. We give our customers the VIP treatment, and every bike we build is project managed by a member of the speed shop. Communication is essential; we have regular meetings with our clients before and during the build process. →
In the concept stage, mood-boards are often used to visualise the ideas. The Speed shop's recent investment in the expansion of the fabrication department has allowed us to design and create a number of products, including fenders, gas tanks, handle bars and exhausts to name but a few.
Having this flexibility and the trained staff to work these machines enables us to push the boundaries of custom bike building. Creating a part that is unique complements the Speed Shop’s ethos on custom building. We want every bike to have a piece of its owner's soul within it.
Our experienced technicians are a rare breed who take their work home. Their passions include bicycles, pit bikes, trials, speedway, motocross and all things on two wheels. Being able to draw upon these influences means that Shaw Speed & Custom have a passionate, knowledgeable and flexible work force. In the last two years since the success of the Bell & Ross “Nascafe Racer” which has been pictured in over 50 magazines worldwide, Shaw Speed have also worked with Ralph Lauren, Rockstar, Playboy, Carole Nash, Barbagallo, Miss Universe, Box Magazine and Peter Lik Photography.
Our motto “Rideable Customs” means exactly that, custom-built bikes that are rideable.


text:
SweetHoney - Dreamer Layette - Terrific
Dreamer Layette - Terrific
Lightweight and silky-smooth - her loungewear will be the unofficial staycation uniform of 2018!
SweetHoney - There Will Never Be A More Beautiful You
- Sizes NB - 2T
- Ruffles on bottom for added flair (ruffles have been adjusted so that they fit properly across the back)
- Zipper closure in the front, covered by a ruffle
- Fold-over hand and feet mitts
Each item is made with lots of detail, uniqueness, and your little girls in mind. Because of this, the chosen fabrics for each item can have slight, natural differences in the texture, placement, and color. These variations are not considered flaws and we believe they add to the character and uniqueness of each item we make.


Electric control panel
With simple monitors, only one pair of cables to transmit power has necessary previsions to switch whereas for complex monitors along with the power carrying cables, it is necessary to make additional cables to transmit signals.
Control panels are manufactured prior to the approvai of the wiring diagrams by our client which is always made-on-order, by using high quality certified equipment accordingto CEI41/S andCEI17-13 (EN 60439-1) Low-voltage switchgear and control gear assemblies-standards. After realization of each control, the tests prevised at said regulations performed and a conformity certificate is always drawn up.
ATEX versions of local or remote control panels are available on request.
Depending on the motors used, there is no distance limit between the control panels and the monitors. Of course, sections of the cables are calculated accordingto the distance between the control panels and the monitors.
Programmable Logic Control (PLC) based control panels with CPU and additional modules are available when needed to control the monitors for complex logical functions.
Control panels are made out of powder coated steel metal materials and are normally designed for indoor use. Special materials for ATEX environment or Stainless steel controlling cabinets are available from our product range up to IP65 protection class.