DE1769795C3 - Process for the production of polyurethanes - Google Patents

Description

Crammed with

In the DT-AS 16 94 080 further provides a process quality Eige ^ns J ^aft _r ^s findunaseemäß to comparable

for the production of crosslinked polyurethanes, also because of these he ^ndu "ff ^ '^^ p ^

wrote, which by reaction of hexanediol-turning polycarbonates m polyesters or rl

1.6 polycarbonate from diphenyl carbonate and hexane can ethers 40 eingese ^tet * "™™ ·

diol with diisocyanates and chain extenders- The production, ^the ^ ° ^α '^ ^Γ ^ _{ε [}

will hold. These elastic plastics are usually drawn by dissolving the

In addition to good mechanical properties, there are no unsaturated connections

good resistance to hydrolysis. With a table made of polycarbonate and attached po ^ ynu η

Hydrolytic aging of these plastics for a day at 45 saüon with the addition of rad.kalb.lde ^ njjr In ^ atoi «sn JMan

70 ^c C and 95% humidity takes place in most can also proceed ^ " ⁿ ^ £ ™ ™

Cases only a slight decrease in the mechanical activator among polymers

Properties, such as strength. In Aus the aliphatic

exceptional cases in which even a small increase in is also possible

Strength of 3 to 5 kg was observed, this 50 aliphatic polycarbonate lies ^^^^

Size within the scope of the measurement error. to bring and then the monome «or mono

fd the side ιversüindl ch can be added

size within the scope of the measurement error. to bring and then the monomial

It has now been found, surprisingly, that merengem.sch add. Page ιversüindl ch can

one obtains polyurethanes which, after 14 days of hy- man, the polymerisation process from case to case

dll bi 7O ⁰ C d 95% humidity the technical requirements pmeasure, ^ more usual

Polyurethanes are obtained which, after 14 days of hy- man, polymerize

drolysenalterung at 7O ⁰ C and 95% humidity pmaß the technical requirements

greatly improved mechanical properties vary in 55 ways; this »U also u ^d '\ ^to

wise when looking at such aliphatic polycarbonates ^^^^^^^. ^^^

with at least two hydroxyl groups with Polviso 5 and 180 C lie. The «^» Ι ^^^

Cyanates and, where appropriate, chain extenders are present in the polycarbonates

^y se TZT ⁸ in which earlier polymers or Mischpoly- as homopolymers suspender Depending on the choice

Men ates of polymerisable unsaturated compounds of the monomers or the ahphaüschen po ^ onates

fertilize in situ. Depending on the situation, they can also be partly or wholly in Jm Po ^

Nature of the carbonate dissolved in the aliphatic polycarbonate or partly or wholly as

The polymer formed can both be present, for example, from a graft polymer. v-rhinduneen

the tensile strengths as well as the cold strengths as polymerizable unsaturated VJ ^ joints

the polyurethanes are increased. For example, such connections are one of the following: or

wise as polycarbonates, in which acrylonitrile poly- several radical «* Ρ? ^ ™ ^? ^1βΓ ^ ™ °° PPJ ^ S

has been merized to obtain plastics that contain after gene. Acrylmtn are particularly worth mentioning

14 days of hydrolysis aging significantly higher solid and methyl, ethyl, butyl acrylate. In Kan

3 4

According to the invention, vinyl aromatics, such as polycarbonates, can also be prepared by the known processes Styrene, or core or side chain substituted with polyisocyanates and chain extensions or Styrenes, such as a-methylstyrene, mentioned, or olefin crosslinking agents in high-quality plastics superhydrocarbons, such as ethylene, also vinyl esters, how to be performed. One can, for example, the invented vinyl acetate, Vinyl chloride or vinylidene chloride, with polycarbonates to be used according to the invention called. The use of polyvinyl compounds, an excess of diisocyanates and implement such as divinylbenzene, triallyl cyanurate or Glykoldi- then low molecular weight compounds such as methacrylate, is also possible. Furthermore, there are also glycols, diamines or water in such a product those unsaturated compounds that still add quantitative proportions that after the reaction are suitable reactive NCO groups are still present with isocyanates or other compounds which are necessary for the reactants Groups included, such as networking, are available. That way you can Oxyäthyl- or oxypropyl (meth) acrylate, acrylamide, moldings are poured during reheating Methacrylamide N-methylol allyl ether, methacrylamide solidify and their final properties on-N-methylol methyl ether, Glycidyl (meth) aa-ylate or take. If you do without a longer post-heating time Acrylic allylesians. The unsaturated compounds 15 after the casting process result in products that can also be used in a mixture with one another and stored under exclusion of moisture. Thermoplastic deformed at any later point in time

In general, aliphatic polycarbonate can be used. This way you can as well nat 0.5 to 60 percent by weight, preferably 1 to 30 Ge products with different degrees of hardness and high percent by weight, of polymerizable, unsaturated elastic properties are obtained, bond released and after the addition of the polymerization one chooses the proportions between the

initiator, optionally with the exclusion of air polycarbonates, the low molecular weight chain oxygen, brought to polymerization with stirring. lengthening agents and the diisocyanate in such a way that, after the reaction, hydroxyl groups are still present in front of the polymerization initiator at room temperature, so that storable thermoplastics of the unsaturated compound are formed and this solution dissolves products that can be processed on the roller, at elevated temperature (reaction temperature) with and, for example, after the addition of further diisogutemic stirring, monocyanate, in particular dimeric 2,4-toluene diisocyanate, is added dropwise to the aliphatic polycarbonate. The anat that is still present after the polymerization change into the crosslinked, elastic state. Monomers are optionally removed in vacuo at 30 The above storable hydroxyl temperatures up to 130 ⁰ C. containing products can be used not only with diiso-

As polymerization initiators, the cyanoates are suitable, but also, for example, with sulfur, Licherweise used radical formers, for example peroxides or formaldehyde are crosslinked. Purpose perester, Percarbonates, hydroperoxides or peroxides are moderate in that the hydroxyl groups are contained Type lauroyl peroxide, benzcyl peroxide or dietary chains contain built-in components that cumyl peroxide, or nitrogen-containing radical formers, with the compounds mentioned with crosslinking such as azodiisobutyronitrile. Even redox systems, how can react. These components are purpose-benzoyl peroxide-dimethyltoluidine, can be used moderately by means of a low molecular weight, bifunk. Likewise, an additional tional hydroxyl compound is optionally incorporated, initiation with the help of high-energy rays in 40 For example, by implementing the Consideration. The radical generators are generally included in the polycarbonates to be used according to the invention Quantities from 0.01 to 15 percent by weight, preferred glycerol monoallyl ether and diisocyanate products, 0.1 to 5 percent by weight, based on the poly which can be crosslinked with sulfur. When replacing the merizable unsaturated compound, used. Glycerol monoallyl ethers by n-dioxäthyltoluidin

As polyisocyanates to be used according to the invention or by N, N'-bismethyl-bis- / I-hydroxyethyl-4,4'-dicyanates, diisocyanates are preferred, such as aminodiphenylmethane products are obtained which, for. B. 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate are crosslinkable with formaldehyde. If one uses as cyanate, 2,4- or 2,6-toluylene diisocyanate, as well as 4,4'-diphenylmethane diisocyanate as diisocyanate, then any mixture of these isomers, p-xylylene diisocyanate, results in products that can be crosslinked with peroxides, cyanate, 4,4'-dimethyl-1,3-xylylene diisocyanate, cyclo-50
hexylene-4,4'-diisocyanate, m- or p-phenylene diisocyanate

cyanate, 1-alkylphenylene-2,4- or 2,6-diisocyanate, example 1

3 - («- Isocyanato-ethyl) -phenyl isocyanate, 2,6-diethyl-

phenylene-1,4-diisocyanate, diphenylmethane-4,4'-diiso- In 200 g one of hexanediol-1,4-polycarbonate and

cyanate, diphenyldimethylmethane - ^^ '- diisocyanate, di- 55 acrylonitrile and in situ polymerization with hydrazoisophenyl ether 4,4'-diisocyanate or naphthylene-1,5-di-butyric acid nitrile obtained polyhydroxyl compound isocyanate. Also tri- or polyfunctional isocyanates (3.35% acrylonitrile; OH number 67), produced by can also be used, e.g. B. 2,4,6-triiso dissolving 5 g of acrylonitrile and 0.1 g of azodiisobutyrocyanatotoluene. nitrile in 100 g hexanediol polycarbonate with subsequent

60 Bender polymerization under N ₂ at 80 ° C and de-chain extenders or crosslinking agents, which may also be used according to the invention, remove the residual monomers in vacuo mm Hg 85 ig molecular weight up to 500 and z. B. glycols, 4,4'-diisocyanatodiphenylnu; than stirred. The Temwie 1,4-butanediol, or diamines such as 3,3'-dichloro temperature rises to 137 ⁰ C. After about 15 minutes 4,4'-diaminodiphenylmethane, represent. Water 65, 18 g of butanediol- (1,4) is added to the melt as a chain extension ·· or crosslinking agent, then the homogeneous mass is poured into the medium in question. To form. After 24 hours of post-heating at 100 ° C

The modified to be used according to the invention gives a material with the following properties:

After 14 days of hydrolysis aging at 70 ° C / 95% humidity

Tensile strength, kg / cm ² 239 255

Elongation at break, % 310 297

Permanent elongation,% 30 21

Tear strength, kg / cm 55 44

Shore hardness A 91 91

Resilience to impact 34 34

Example 2

According to the test conditions given in Example 1, 200 g of a 1,6-hexanediol polycarbonate, 10.5% acrylonitrile and 0.5% by weight methacrylamide produced polyhydroxyl compound (OH number 60), prepared analogously to Example 1, with 81.5 g of 4,4'-diisocyanatodiphenylmethane and 18 g of butanediol (1,4) reacted. The material obtained has the following properties:

Tensile strength, kg / cm ² 255

Elongation at break,% 267

Permanent elongation,% 44

Tear strength, kg / cm 46

Shore hardness A 94

Resilience 33

After 14 days of hydrolysis aging at 70 ° C / 95% humidity

293 305 42 44 95 35

Example 3

Under the given conditions of Example 1 200 Grams of hexane-l, 6-A polycarbonate and 30 weight percent butyl acrylate, prepared by adding to a heated at 120 ⁰ C amount of 70 g of hexane diol (molecular weight 2000)

so in the course of 1.5 hours 30 g of a solution of 2 g of azodiisobutyronitrile has been dropped into 98 g of butyl acrylate, prepared polyhydroxyl compound (OH number 44.8) reacted with 80 g of 4,4'-diisocyanatodiphenylmethane and 19.8 g of 1,4-butanediol. The obtained material has the following properties:

212 After 14 days 292 Hydrolyses 30th aging at 50 70 ° C / 95% air 93 humidity Tensile strength, kg / cm ² 34 223 Elongation at break, % 328 Permanent elongation,% 25th Tear Strength, kg / cm 45 Shore hardness A 93 Resilience 34

Claims (1)

than before. The polymerization vou ζ B Acrylsaureestern in aliphatic polycarbonates b ^ ICT a significant improvement in Kalte- ζ B Acrylic acid esters in aliphatic polycarbonates Patent claim: b ^ its a significant improvement in the cold Process »IMdta. vo "Po ^ Chan" ^^. ₈ ^, ^ 1Αί'ΑΐηΓνοη'ρ of at least two hydroxyl groups aufwei- 5 ^findun S ^ ™ ° ^gl! Lji _ünsdlten properties which even send aliphatic polycarbonates with a uretnane ⁿ ™ ^l & _dterung, at least erhalteu, Molekujarfewicht 800-3000, polyisobutylene during the H ^ WSS ^ J ^^ _who the. The cyanates and, if applicable, chain lengthening agents ^{in the} fg _m | ß _invention thus differ or crosslinking agents under shaping, because FroauKie according to * polyurethane plastics, characterized by that as ahpha- ₁₀ of the bjgr ^ gmnjj- ^ y ^; tables polycarbonates such are used, their. ^El S ^ chat ^ bi α wa overall, however which have been prepared by transesterification of polyols with di- tert rung.f ^ term Falk ernau as aryl carbonates and in ^^^ ΓππΤ to a process for Herdenen polymerizable compounds ungesätt.gte The ^ f ^ _r X ^findun _{NEN of} at least two hy- have been polymerized in situ under aliphatic optionally Pfropfpolymensat- ₁₅ SJJ ^^ SSSLn Polycarbobildung. droxyIgnippen ^ a _{molecular weight between a 800} and 3000 polyisocyanates and optionally chain extenders or cross-linking agents to form ₂₀ gebung, characterized in that, as such, be used a iphatische polycarbonates which durcn Transesterification of polyols with diaryl carbonates and in which polymerizable unsaturated compounds have been polymerized in situ with optionally graft _{poly a} , merisatbüdung The polycarbonates to be used for this purpose, which preferably have an average molecular weight of The manufacture of polyurethane plastics from about ² ^. ^^ Α Polyhydroxy compounds in which polymerizable ^^^^^ So ^ H ^ BXiJi-1,6, Neunsaturated compounds have been poymens.ert in situ 30 compounds ^ e Butenöio _{aryl carbonates} ,