CN104254550B - Modified polyacetal is carried out with imidized acrylic - Google Patents
Modified polyacetal is carried out with imidized acrylic Download PDFInfo
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- 229920002866 paraformaldehyde Polymers 0.000 title claims abstract description 86
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 110
- 239000002253 acid Substances 0.000 claims abstract description 56
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 125000004432 carbon atoms Chemical group C* 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims description 22
- 229920001519 homopolymer Polymers 0.000 claims description 13
- -1 cyclic imide Chemical class 0.000 claims description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- BAVYZALUXZFZLV-UHFFFAOYSA-N methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- XJRBAMWJDBPFIM-UHFFFAOYSA-N Methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000000172 allergic Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 45
- 239000000463 material Substances 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- 150000008064 anhydrides Chemical class 0.000 description 12
- 239000000155 melt Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000003949 imides Chemical class 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 150000004965 peroxy acids Chemical class 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 238000011068 load Methods 0.000 description 7
- 229920001169 thermoplastic Polymers 0.000 description 7
- 210000003128 Head Anatomy 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 230000000996 additive Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N Dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N N#B Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- 229920002803 Thermoplastic polyurethane Polymers 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006266 etherification reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 230000002378 acidificating Effects 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 230000000630 rising Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229960000458 Allantoin Drugs 0.000 description 2
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N Glutarimide Chemical compound O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000000473 carbonimidoyl group Chemical group [H]\N=C(/*)* 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 238000009527 percussion Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011528 polyamide (building material) Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000003252 repetitive Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LCJRHAPPMIUHLH-UHFFFAOYSA-N 1-$l^{1}-azanylhexan-1-one Chemical compound [CH]CCCCC([N])=O LCJRHAPPMIUHLH-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 210000001643 Allantois Anatomy 0.000 description 1
- 210000001736 Capillaries Anatomy 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N Diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N Isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N M-Cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229920002521 Macromolecule Polymers 0.000 description 1
- 210000000214 Mouth Anatomy 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-Butylamine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920001721 Polyimide Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010928 TGA analysis Methods 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N ethyl amine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002085 persistent Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001888 polyacrylic acid Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003389 potentiating Effects 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000003014 reinforcing Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
As herein described is compositions, and the number-average molecular weight that described compositions comprises (a) 92 to 99 percentage by weight is 65, the polyformaldehyde of 000 to 250,000g/mol；(b) imidized acrylic obtained by processing acrylic polymer by monoalkylamine of 1 to 8 percentage by weight, the wherein percentage by weight of a and b combined wt based on them meter, and monoalkyl has one to five carbon atom, imidizate degree is 20% to 100%, and 0 that acid content is imidized acrylic is to about 2 percentage by weights.Described compositions has the heat deflection temperature more significantly higher than pure polyformaldehyde.Also describe by method that (a) and (b) increase the heat deflection temperature of described herein POM compositions is blended, wherein relative to the compositions of the same melt mixing without (b), the compositions of gained melting mixing has the time to 5% creep strain of 200% increase or bigger.
Description
Summary
The present invention relates to use imidized acrylic as the modifying agent of polyformaldehyde to improve its high-temperature behavior.
Polyformaldehyde [POM] compositions comprises the cyclic oligomer of formaldehyde or formaldehyde (such as threeAlkane) homopolymer, and/or
The copolymer of the cyclic oligomer of formaldehyde or formaldehyde.POM homopolymer has through esterification or the end group of etherification reaction end-blocking.?
In POM copolymer, oxyalkylene group contains at least two adjacent carbon atom in main chain, and end group can be hydroxyl envelope
End or through esterification or etherification reaction end-blocking.The ratio of comonomer can be at most 20 percentage by weights.
Containing the POM compositions of higher molecular weight POM (that is, between 50,000 and 100, between 000), can be used for by often
For thermoplastic technology (such as compression moulding, be molded, extrude, be blow molded, solution spinning, impressing and hot forming) in any one
Prepare goods.The goods being made up of this class higher molecular weight POM compositions have desired physical property, as rigidity, intensity,
Toughness, dimensional stability and solvent resistance.
POM compositions is permissibleTrade name is commercially available from Du Pont, and produces for automotive industry, industry
Industry, electronics industry and consumer goods industries.
Unmodified POM has heat deflection temperature [HDT] and about 3000 megapascal (MPa)s of about 97 DEG C to 100 DEG C
The bending modulus of [MPa].For most engineer applied, both performances are the most not high enough.Increase the rigidity of POM and HDT
Conventional method is once for adding glass fibre.Although increasing HDT, but add glass fibre and add weight, improve not
Good appearance, molding difficulty and anisotropic properties (as shunk), and reduce toughness.
United States Patent (USP) 2,146,209,3,284,425,4,169,924 and 4,246,374 disclose polyglutarimide, also
It is referred to as imidized acrylic polymer or polyacrylic acid imide.United States Patent (USP) 4,246,374 and 4,217,424 describes
Mixing imidized acrylic polymer and other material, such as impact modifier, pigment, fiber, stabilizer, lubricant
Deng.United States Patent (USP) 4,255,322,4,595,727 and 5,502,111 discloses the PVC of the heat deflection temperature with improvement with poly-
The blend of glutarimide.
Imidized acrylic has been used for modified polyamide to improve their melt flows, melt strength, to draw
Stretch intensity and modulus.Compared with pure imidized acrylic, polyamide is compatible with imidized acrylic
Property blended polymer has impact resistance and the ductility of improvement.Elevated operating temperature is added in the nylon of relatively low operating temperature
Imidized acrylic causes the operating temperature that improve nylon.Imidized acrylic and nylon and often
The compatibility blended polymer of rule impact modifier shows the imidizate third more modified than conventional impact modified dose by equivalent
The shock response (seeing United States Patent (USP) 4,415,706 and 4,874,817) that olefin(e) acid resinoid improves.
The compositions having made imidized acrylic resin and comprise POM and thermoplastic polyurethane is blended, to provide improvement
Die shrinkage, simultaneously the most still retention performance (such as rigidity, elongation and toughness) available balance (see United States Patent (USP) 5,318,
813 and European patent EP 0424755).United States Patent (USP) 4,727,117,4,954,574,5,004,777 and 5,264,483 disclosure
50/50 blend of POM and imidized acrylic resin.Japan patent applicant announce JP1990-015585 discloses poly-
Glutarimide and the blend of polyacetals, to provide impact resistance and mobility, keep the heat of polyglutarimide to scratch simultaneously
Qu Wendu.German patent application DE4132638 discloses the blend of POM and imidized acrylic.
Wishing to develop polyformaldehyde composition, described compositions has the heat deflection temperature of increase, in room temperature with less than poly-first
Rigidity/the modulus increased at a temperature of the rising of the fusing point of aldehyde fusing point, the top increased under given rigidity use temperature, and
The long-term creep reduced at elevated temperatures.Also being intended to develop the compositions with these characteristics, described compositions has and changes
Kind heat stability, antidecomposition at elevated temperatures.
As herein described is thermoplastic compounds, described compositions comprise following, substantially consist of or by following
Preparation:
A () combined wt meter based on (a) He (b), the number-average molecular weight of about 92 to about 99 percentage by weights is 20,000
Polyformaldehyde to 250,000g/mol；With
(b) combined wt meter based on (a) He (b), about 1 to about 8 percentage by weight by with monoalkylamine process third
Olefin(e) acid base polymer and the imidized acrylic that obtains, wherein monoalkyl has one to five carbon atom, acid imide
Change degree is 20% to 100%, and 0 that acid content is imidized acrylic is to about 2 percentage by weights.
It should be noted that described compositions is substantially free of thermoplastic polyurethane.Preferably, by processing by methyl amine
Polymethyl methacrylate obtains imidized acrylic.Preferably, imidized acrylic with about 1 to
The amount of about 5 percentage by weights is present in compositions.
There is also described herein the goods comprising compositions described herein.Described goods have according to ASTM D-648 mensuration
Exceeding the heat deflection temperature of the heat deflection temperature of reference standard goods, wherein said moulded products has phase with reference standard goods
Same shape and structure, except reference standard goods are prepared by the polyformaldehyde composition without imidized acrylic.
The method that there is also described herein the moulded products comprising compositions for preparation, described method includes:
(1) by the first polyformaldehyde composition and imidized acrylic melt blending, to provide as above
Molten thermoplastic compositions, wherein said first acetal resin as described in component (a) above, wherein said imidizate third
Olefin(e) acid resinoid is as described in component (b) above；
(2) melt composition is made to form required shape, and
(3) melt composition is made to cool down, to provide moulded products；
Wherein moulded products has the heat of the heat deflection temperature exceeding reference standard goods measured according to ASTM D-648
Deflection temperature, wherein moulded products and reference standard goods are of similar shape and structure, except reference standard goods are not by
Prepared by the first polyformaldehyde composition containing imidized acrylic.
There is also described herein the method increasing heat deflection temperature, described method includes:
Melting mixing
The imidized acrylic of (a) 1 to 8 percentage by weight,
It has
Acid content and
Imidizate degree, and
Obtain by processing acrylic polymer by the monoalkylamine with monoalkyl；
B the number-average molecular weight of () 92 to 99 percentage by weight is 50, the polyformaldehyde of 000 to 250,000g/mol, and
(c) optionally, one or more other additives,
To obtain the compositions of melting mixing,
Wherein:
A the percentage by weight of () and (b) is each based on the combined wt meter of (a) and (b),
Monoalkyl has one to five carbon atom,
Imidizate degree is 20% to 100%,
Acid content is 0 to about 2 percentage by weight of imidized acrylic；And
As measured by ISO899-1, the time to 5% creep strain of the compositions of melting mixing is the phase without (a)
With compositions 200% or bigger.
Detailed description of the invention
Definition and abbreviation
Defined below and abbreviation is intended to for illustrating art that is discussed in book and that stated in claims
The implication of language.
As used herein, article "/a kind of " refers to one/a kind of and more than one/one, and is not necessarily limited
Its indication noun is odd number.
As used herein, term " about " and " for or about " refer to considered amount or numerical value can be designated value or with appointment
Value approximation or certain close other value.This term is intended to express, and similar value causes the equivalent stated in claims
Result or effect.
As used herein, term " include " (comprises, cmprising), " including " (includes,
Including), " have " (has, having), " substantially by ... composition " and " consist of " or these any other
Modification can refer to including of nonexcludability or including of exclusiveness.When these terms refer to the bag of the nonexcludability of key element list
Include, technique, method, goods or during equipment, be not limited to listed elements, but can include that not expressly listed can be maybe intrinsic its
Its key element.Additionally, unless clearly contrary explanation, "or" refer to inclusive or rather than refer to exclusiveness or.Such as, below
In any one be satisfied by condition A or B:A is genuine (or existence) and B be false (or non-existent), A be false (or not depositing
) and B is genuine (or existence) and A and B is genuine (or existence).
When these terms refer to more when including of exclusiveness, and the scope of claims is limited to those by these terms
The novel key element of the present invention that the material stated or step, described material or step appreciable impact are stated.
When these terms refer to when including of complete exclusiveness, these terms do not include being not explicitly stated in claims
Any key element, step or assembly.
As used herein, term " goods " refers to article (item) that are that be not fully complete or that complete, object (thing), object
(object) or be not fully complete or the element of article, object or object that completes or parts.As used herein, when goods are not fully complete
Time, term " goods " can refer in the goods that will be included in and/or will experience further processing to have become
Any article of goods, object, object, element, device etc..As used herein, when goods complete, term " goods " refers to
Live through complete machining thus be applicable to the article of special-purpose/purpose, object, object, element, device etc..
Goods can include one or more element or sub-component, described element or sub-component be partly be done and
Await being processed further or fitting together with other element/sub-component and constitute finished product.Additionally, as used herein, term
" goods " can refer to system or the configuration of goods.
As used herein, describe the term of molecule or polymer meet JIUYUE in 2009 7 daysIUPAC Compendium of Chemical Terminology, term in 2.15 editions (IUPAC).
As used herein, term " additive " refers to add the other component to polyformaldehyde composition as herein described, institute
State component and be different from imidized acrylic as herein described.
Unless otherwise noted, all of percentage ratio, number, ratio and similar quantity define the most by weight.
As used herein, term " for known to those skilled in the art ", " routine " or the word of synonym or phrase
Refer to represent material, method and machine be routine operation known or filing present patent application when technical staff will recognize
Know and arrive as known description.
As used herein, term " polymer " " refer to only different on the number of repetitive macromolecule or high molecular
Set, including oligomer, homopolymer or copolymer.
As used herein, term " copolymer " refers to be comprised copolymerization by the copolymerisation gained of more than one comonomer
Close the polymer of unit.Copolymer can be through consisting of comonomer or through retouching consisting of the amount of comonomer herein
State, such as, " comprise acrylic acid copolymer of ethylene and 18 percentage by weights " etc..This description of copolymer shows copolymerization
Thing comprises the combined polymerization unit (when specifying with specified amount) specifying comonomer.Term " terpolymer " refer to substantially by
The polymer of three kinds of monomer compositions.
As used herein, term " polyformaldehyde " (being abbreviated as POM), " polymethanal polymer " and " polyacetal polymer " refer to
One or more have repetitive CH2The homopolymer of O, copolymer, and these mixture.The end of these polymer
End group group is to be obtained by initiation, termination, or chain tra nsfer group (such as water or alcohols)；Or by chemical reaction, as caused
Ester or ether (including acetas, acetyl group, methyl and methoxyl group) and obtain.
As used herein, term " acrylic resin " refers to acrylate (alkyl acrylate), or methacrylic acid
Ester (alkyl methacrylate), or these any combination of polymer.
As used herein, term " imidized acrylic polymer ", " imidized acrylic " and " poly-penta
Imidodicarbonic diamide " it is used interchangeably and refers to following chemical constitution:
Structure I: imidized acrylic ester or methacrylate polymers:
Wherein R1For C1-C5Alkyl, and
R2For H or CH3
Structure I I: imidizate methacrylate polymers
Wherein R1For C1-C5Alkyl.
As used herein, term " peracid imidized acrylic [IA] " refers to the sour weight with 5 or bigger
The IA of percentage ratio.
As used herein, term " low acid IA " refers to have the sour weight hundred of 4 or less, preferably smaller than 1 percentage by weight
The IA of proportion by subtraction.
As used herein, M be abbreviated as in term " weight average molecular weight "wOr Mw.As used herein, term " number-average molecular weight " contracts
It is written as MnOr Mn.
As used herein, term " polymer " melt mass flow rate ", " melt flow rate (MFR) " or " melt flow index ", contracting
It is written as " MFR " or " MFI ", refers to the polymer composition melt amount at the easy mobility of interior melt of thermoplastic polymers
Degree.It is defined as under alternative set point of temperature, by the pressure applied via alternative weight counterweight of regulation
Power, the quality of the polymer in gram of the capillary tube flowed by special diameter and length in 10 minutes.The method is at mark
Quasi-ASTM D1238-04c is described.Except as otherwise noted, polymer melt mass velocity by gram/10 minutes in units of report
Accuse, and carry out under conditions of 190 DEG C/2.16kg.
Melt flow rate (MFR) is the indirect measurement of molecular weight, and the highest melt flow rate (MFR) corresponds to low-molecular-weight.Meanwhile,
Melt flow rate (MFR) is measuring of melted material fluid ability under stress.Under test conditions, melt flow rate (MFR) is with molten
Body viscosity is inversely proportional to, but it should be borne in mind that the viscosity of this type of material any depends on applied power.A kind of material is in difference
The ratio of two melt flow rate value under weight counterweight is often used as measuring of molecular weight distribution width.
As used herein, term " is substantially free of thermoplastic polyurethane " and refers to less than 1 percentage by weight in compositions, excellent
Choosing is less than the thermoplastic polyurethane of 0.5 percentage by weight.
As used herein, term " heat deflection temperature ", " thermal distoftion temperature ", it is abbreviated as HDT herein, refers to polymer or mould
That temperature that property sample deforms under given load.
As used herein, " the imidizate degree " of term imidized acrylic as herein described refers to anti-with amine
Should be to form the mole of the ester group of cyclic imide part.This term is also with the weight of imide group ring-type in gained copolymer
Amount percentage ratio describes.
As used herein, term " creep resistance ", " deformation of creep " and " to the time of X% creep strain " refer to identical or
The attribute of equivalent, it supports measuring of creep resisting ability for material.Specifically, creep is that solid material delays under the influence of stress
Slowly move or that trend of permanent deformation, and as being exposed to for a long time under great horizontal stress (less than the yield strength of material)
Result and occur.Be heated for a long time and in material near fusing point creep more violent, because creep often raises with temperature
And increase.
Therefore, term " to the time of X% creep strain " is that material experiences X%, as 5% or 7% creep strain spends
Measuring of persistent period, and so measure the creep strain speed in second stage or state creep stage.
As used herein, term " storage modulus E " refers to the component of elasticity of the modulus of material, relative with viscous components.
As used herein, term " MPa ", " mPa " refer to megapascal (MPa) or Megapascal, are measuring of pressure.Such as this
Literary composition is used, term " kPa ", " kPA ", " kPa " refer to kPa or kPa.
As used herein, symbol " % " refers to percentage ratio.
As used herein, term " in ", " m ", " cm " refer respectively to inch, rice and centimetre.
As used herein, term " hr ", " min ", " sec " refer respectively to hour, minute and second.
As used herein, term " lb ", " oz ", " gm ", " kg " refer respectively to pound, ounce, gram and kilogram.
As used herein, term " Tg " refers to glass transition temperature.
As used herein, term " CHN analyser " refers to measure sample elementary composition and measured by equipment three kinds
Essential element: carbon (C), hydrogen (H) and nitrogen (N) obtain that instrument of sample name.Sulfur (S) and oxygen (O) can also be measured.
As used herein, term " standard deviation " refers to standard deviation.
Scope
Except as otherwise noted, any scope as herein described includes its end value the most clearly.Illustrate certain amount, concentration or its
Its value or parameter, as scope, specifically disclose the institute formed by any pair of any range limit and any range lower limit
There is scope, regardless of whether this type of limit value is to being separately disclosed the most herein.Method described herein and goods are not limited to saying
In bright book limit scope time disclosed in occurrence.
Preferably variant
Press method described herein, compositions and system that material, method, step, value and/or scope etc. are disclosed herein
The preferred variant of any variant of product-be whether identified as-be specifically intended to is open includes this type of material, method, step
Suddenly, any combination of any technique of value, scope etc. and goods.For the support accurate and enough for claims offer
Purpose, any combination disclosed in this type of is specifically intended to become the preferred of method described herein, compositions and goods
Variant.
Ordinary circumstance
The POM compositions being to comprise imidized acrylic polymer (IA) as herein described.It is also described that and pass through
Add low acid imide acrylic polymer and (i.e. have 50,000 to 250,000 to improve higher weight POM compositions
The method of creep resistance Mn).
These compositionss and method have the heat-resistant quality of improvement, as increase heat deflection temperature, the softening temperature of increase,
Rigidity/the modulus increased at a temperature of room temperature and the rising less than POM fusing point and the top increased under given rigidity make
Use temperature.Owing to IA has the glass transition temperature more much higher than polyformaldehyde, so the blend of IA and polyformaldehyde improves
The thermostability of POM compositions and other mechanical performance, such as hot strength and thermoplasticity processability.It is surprising that utilize non-
Often the IA of low content just obtains the deflection temperature of raising and the beneficial effect of the rigidity/modulus of increase.
Polyformaldehyde [" POM "]
Polyformaldehyde in compositions described herein includes the homopolymer of formaldehyde or the homopolymer of the cyclic oligomer of formaldehyde, it
End group via esterification or etherification reaction and block；And include cyclic oligomer and other monomer of formaldehyde or formaldehyde
Copolymer, described copolymer produces the oxyalkylene group in main chain containing at least two adjacent carbon atom, their copolymer
End group can be hydroxy-end capped or can block via esterification or etherification reaction.
Polyformaldehyde can be branched or straight chain and substantially have the number in the range of 20,000 to 250,000g/mol
Average molecular weight (Mn).Can be used for the POM in compositions described herein and show the Mn of 50,000 to 100,000, and more preferably
50,000 to 80,000.Particularly preferably number-average molecular weight is about the polyformaldehyde of 65,000.The weight of the POM in blend
Average molecular weight (Mw) can be 50,000 to about 150,000g/mol, preferably 100, and 000 to 150,000g/mol.
Can use normal pore size is 60 and 1000 angstromsBimodal column external member, at 160 DEG C, in metacresol, pass through gel
Permeation chromatography advantageously measures molecular weight.
As the alternative form of number-average molecular weight, melt flow rate (MFR) can also characterize POM used herein.Described herein
Polyformaldehyde suitable in compositions has the melt flow rate (MFR) of 0.1 to 40 gram/10 minutes, as according to ASTM-D-1238, operation
A uses 2.16kg counterweight to be measured at 190 DEG C.Preferably, the POM in compositions described herein has 0.5 to 35 gram/10 points
The melt flow rate (MFR) of clock.It is highly preferred that POM used herein is straight chain, there is the melt flow of about 1 to 20 gram/10 minutes
Dynamic speed.Particularly preferably there is the POM of the melt flow rate (MFR) of about 1 to 5 gram/10 minutes or about 10 to 20 grams/10 minutes.
POM in compositions described herein can be homopolymer, copolymer, or these mixture.POM homopolymer is excellent
Choosing, because it has bigger rigidity and intensity.Preferably POM-H Acetal homopolymer includes that its terminal hydroxyl is anti-by chemistry
Those forming ester or ether (preferred acetas or methoxyl group respectively) should be blocked.United States Patent (USP) 2,998,409 describes second
The preparation method of the POM homopolymer of acid esters end-blocking.
POM copolymer can comprise one or more comonomers being usually used in preparing POM compositions.Copolymerization list more often
Body includes the alkylene oxide of 2 to 12 carbon atoms and their cyclic addition products with formaldehyde.Compositions described herein
In the amount of comonomer less than 20 percentage by weights, preferably more than 15 percentage by weights, and most preferably about 2 weight
Percentage ratio.Most preferably comonomer is oxirane.
POM compositions as herein described can comprise well-known may be added to that those additives of polyformaldehyde, composition and
Modifying agent, such as stabilizer and antioxidant.
Imidized acrylic
Imidized acrylic polymer has following chemical constitution and a formula:
Structure I: imidized acrylic ester or methacrylate polymers:
Wherein R1For C1-C5Alkyl, and,
R2For H or CH3
Structure I I: imidizate methacrylate polymers
Wherein R1For C1-C5Alkyl.
See for example United States Patent (USP) 3,284,425,4,246,374,4,518,717,4,727,117 and 5,110,877.
It should be noted that imidized acrylic comprises cyclic imide unit.Imidized acrylic
Polymer can be by making ammonia or primary amine and acrylate or methacrylate homopolymer or copolymer (such as poly-(metering system
Acid methyl ester)) prepared by reaction, and this reaction is produced ring-type acyl by amine and the condensation of on acrylic polymer two adjacent ester groups
Imine group.The mole of the ester group being reacted to form cyclic imide part with amine is referred to as imidizate degree, and this can also
In gained copolymer, the percentage by weight of ring-type imide group describes.
It is methylamine for processing the preferred primary amine of acrylic polymer in above-mentioned imidization reaction, but can use relatively
High aliphatic amine.Other amine includes such as ethamine, 2-aminopropane. and butylamine.
Acrylic polymer can be poly-(methyl methacrylate) or poly-(acrylic acid methyl ester .), the most poly-(metering system
Acid methyl ester).Other polymethacrylates or acrylate copolymer can replace poly-(methyl methacrylate) to use, but can
Can be more worthless, because they have relatively low glass transition temperature [Tg].These polymer are except containing methyl-prop
Olefin(e) acid ester or acrylate monomer, it is also possible to make the other ethylenic unsaturated comonomer of small amount and they combined polymerizations.This
The most other monomer can be such as styrene, acrylonitrile, vinyl acetate, ethylene, butadiene and methyl vinyl ether.When with
In time preparing imidized acrylic ester, methyl methacrylate or acrylic acid methyl ester. are other selected from benzene second with at least one
The copolymer of the comonomer of alkene, acrylonitrile, vinyl acetate, ethylene, butadiene or methyl vinyl ether is preferably containing at least
About 40 percentage by weights, preferably at least 60 percentage by weights, and the methacrylate of more preferably at least 80 percentage by weights
Or acrylic ester unit.
Suitably imide amination polymer includes imidizate poly-(methyl methacrylate) or poly-(acrylic acid methyl ester .), first
Base acrylic acid methyl ester. or acrylic acid methyl ester. and the imidized copolymers of those comonomers as listed above, wherein gather
(methyl methacrylate) and methyl amine are reacted.It is different from imidized acrylic in the PVC blend of United States Patent (USP) 4,255,322
The molecular weight of acid resin-usual 100,000 to 200,000-and imidizate degree-20% to 60%, combination as herein described
The imidized acrylic that thing has has the preferred molecular weight of 20,000 to 200,000, and 20% to 100%,
Preferably 60% to 100%, more preferably 80% to 100%, the imidizate degree of most preferably 90% to 100%.
Depending on the imidizate degree of starting polymer, imidized acrylic polymer as herein described can comprise change
Change amount do not change ester group, carboxyl and end-blocking carboxyl.As the acyl with (methyl) acrylic polymer of ammonia or primary amine reaction
The by-product of imidization, anhydride and acidic group are formed on polymer chain, and are reported as when forming acid imide unit
Intermediate.When imidizate degree is more than 95% and close to 100%, it is present in the acid on gained imidizate product and anhydride
The amount of unit reduces.When the imidizate degree of imidized acrylic polymer described herein is 95% or less, as
Acid and the amount of anhydride functionality that the typical consequence of reaction is present on polymer chain are probably unexpected, because it is the most right
The characteristic of polyimides has a negative impact.Such as, the acid on imide amination polymer described herein and anhydride functionality can change
Become the compatibility of polymer and other thermoplastic polymer.
The number reducing the acid on imidized acrylic polymer and anhydride group is known and such as beautiful
State's patent 4,727,117,4,954,574,5,004,777,5,110,877,5,264,483 and 5,548,033 and the U.S. are special
Profit Shen Qing Publication 2007/0055017 has been discussed.United States Patent (USP) 4,727,117 disclose a kind of method, wherein with can be by
Acid and anhydride group are converted into non-acid or non-anhydride group and can not be remaining with the agent treated of acid imide unit process
Acid and anhydride group.These reagent include alkylating agent and esterifying agent, such as alkyl orthoformate or dimethyl carbonate.As by depositing
Indicated by the percentage by weight of the acidic group (such as methacrylic acid unit) being in polymer, acid content is 0 to 10 weight percent
Ratio, and preferably 0 to 2 percentage by weight.
Rohm and Haas Company (Philadelphia, PA) had previously supplied some imidized acrylic
Resin, includingHT-510 grade, for being blended with PVC；AndEXL-4000 etc.
Level, has the resin family of higher glass transition temperature, for being blended with other engineering resin.Imidized acrylic tree
The Tg of fat changes with the imidizate degree of starting propylene acids polymers, and Tg reduces when imidizate degree increases.HT-510 has an at a fairly low Tg, about 130 DEG C.EXL-4000 family has 140 DEG C
To the report Tg value of 170 DEG C.Zeng JiangResin and nylon 6, Merlon, acrylonitrile/phenylethylene/butadiene
Be blended with styrene/acrylonitrile resin and poly-(PETP), thus increase resulting composition thermostability or
Melting intensity, and improve optical characteristics, or it is used as the carrier of pigment and other additive.
EXL-4000 grade resin can have the carboxyl less than 1 percentage ratio to about 10 percentage ratios；Some
Anhydride group in a small amount can also be comprised.As explained above, carboxyl be clearly during imidization reaction formed and can
Can be inevitable.But, those carboxyls of these resins of some grades are likely to block through esterification.
Additive
Compositions as herein described is except including POM and imidized acrylic polymer, it is also possible to include as conventional
In other additive, modifying agent and the composition of polymer arts, described additive, modifying agent and composition include stabilizer and are total to steady
Determine agent (such as United States Patent (USP) 3,960,984,4,098,843,4,766,168,4,814,397,5,011,890 and 5,063,263
In disclosed those), antioxidant, pigment, coloring agent, UV stabilizer, toughener, nucleator, glass, mineral, lubrication
Agent, fiber, reinforcing agent and filler.The stability of polyformaldehyde composition can be had a negative impact by some pigment and coloring agent, but
It is that the impact of the physical characteristic on them is the least.Preferably heat stabilizer, in United States Patent (USP) 5, is described in 011,890, Qi Zhongju
Acrylamide is most preferred.
The method increasing heat deflection temperature
Increase creep resistance and show as increasing the heat deflection temperature of polyformaldehyde.Increase creep resistance to depend on adding low acid
IA.Therefore, add low acid IA improve creep resistance and increase heat deflection temperature.
By making rectangle specimen stand the temperature that constant load applies steadily to increase simultaneously, measure the heat of thermoplastic
Deflection temperature.Flexure to temperature during preset value of the crossbeam wherein loaded under flexing is referred to as heat deflection temperature (HDT).At this
Under a little test conditions, the actual strain that sample is experienced is typically smaller than 1% and is substantially flexibility.The increase of heat deflection temperature
Rigidity corresponding to improving with the temperature of compositions retains.
It is also required to improve rigidity to improve the creep resistance of POM compositions.Therefore, when standing the temperature steadily increased
The raising of POM compositions rigidity reflects the increase of heat deflection temperature and the raising of creep resistance.
It is at high temperature and high load capacity that tensile creep described below measures, and carries out under 90 DEG C and 25MPa.In these conditions
Lower Reducing distortion retains corresponding to more preferable rigidity, and the rigidity being similar to observe during heat deflection temperature is measured retains.
But, measure compared to HDT, measure creep resistance with more harsh stretching mode here, wherein sample is whole
Cross section is exposed to same load.Additionally, until total accumulative strain is just tested at least 7%.This is at HDT than generally
That observes in test strains much bigger strain.Therefore, creep resistance here measures and reflects the tightened up of rigidity reservation
Test, therefore more strongly shows the increase of HDT for compositions described herein.
The method increasing heat deflection temperature as herein described includes the step of the following material of melting mixing:
The imidized acrylic of (a) 1 to 8 percentage by weight, its
Have
Acid content and
Imidizate degree and
Obtain by processing acrylic polymer by the monoalkylamine with monoalkyl；
B the number-average molecular weight of () 92 to 99 percentage by weight is 50, the polyformaldehyde of 000 to 250,000g/mol, and
(c) optionally, one or more other additives,
To obtain the compositions of melting mixing,
Wherein:
A the percentage by weight of () and (b) is each based on the combined wt meter of (a) and (b),
Monoalkyl has one to five carbon atom,
Imidizate degree is 20% to 100%,
Acid content is 0 to about 2 percentage by weight of imidized acrylic；And
As measured by ISO899-1, the time to 5% creep strain of the compositions of melting mixing is the phase without (a)
With compositions 200% or bigger.
In addition to the time shown to 5% creep described in earlier paragraphs, these methods can also show root
The heat deflection temperature measured according to ISO-751/-2 is 20% or bigger of the same combination without (a).Additionally, described herein
In any one in method, imidized acrylic can comprise cyclic imide unit and/or with 1 to 5 weight percent
The amount of ratio is present in the compositions of melting mixing.
Additionally, in any one in methods described herein, can be by processing selected from following acrylic polymer with methylamine
Compound and obtain imidized acrylic:
Poly-(methyl methacrylate)；Poly-(acrylic acid methyl ester .)；Acrylic acid methyl ester. is other selected from benzene second with at least one
The copolymer of the comonomer of alkene, acrylonitrile, vinyl acetate, ethylene, butadiene or methyl vinyl ether；And metering system
Acid methyl ester is other selected from styrene, acrylonitrile, vinyl acetate, ethylene, butadiene or methyl vinyl ether with at least one
The copolymer of comonomer.In these methods, preferred acrylic polymer can be poly-(methyl methacrylate) and/
Or imidized acrylic can obtain by processing poly-(methyl methacrylate) with methylamine.
Additionally, in any one in these methods as herein described, polyformaldehyde has 50,000 to 80,000g/mol's
Number-average molecular weight and be selected from homopolymer, copolymer, and these mixture.Additionally, in these methods as herein described
In any one in, imidizate degree can in the range of 60% to 100%, preferably 80% to 100%, and more preferably 90%
To 100%.
Prepare POM compositions as herein described
POM compositions as herein described preferably by the granule of each component or similar articles are rolled or mix and
Make.In any case mixing, each component all should be via any mixing facilities melt blending, and described equipment can be higher than poly-
The softening point of compound blend components and develop high shear within the temperature range of significantly degraded is put less than it.This kind equipment
Example include rubber mill, banbury (such as " Banbury " banbury and " Brabander " banbury), with can be by outside
The single-blade of the cavity of heating or frictional heat or multiple-cutting-edge banbury, " Ko-kneaders ", multitube mixing roll are (such as
" Farrell Continuous Mixers "), injection machine and extruder, wherein extruder can be single screw extrusion machine and double spiral shells
Bar extruder, double screw extruder includes rotating Vortex formula and heterodromy.These equipment can be used alone, or with static state
Agitator, batch mixing head and/or the plurality of devices that designs for increasing internal pressure and/or intensity are with the use of, these equipment bags
Include valve, gate or screw rod.
Preferably with continuous mixing equipment to realize the uniform mixing of blend components, possess the efficiency of maximum, denseness
And the uniformity.Extruder is that most convenient uses because their handling capacities are high, can modular and being easy to assemble, optional
Select multiple mixing screw and be easy to control and maintain method temperature.Especially preferably double screw extruder, is particularly equipped with
Those of high intensity mixing section (such as reverse pitch element and kneading member).
Comprise the goods of POM compositions as herein described
The moulded products comprising POM compositions as herein described can be made up of any one of some universal methods,
Described method include compression moulding, be molded, extrude, be blow molded, solution spinning, film forming (including casting films or blown film techniques) become with heat
Shape.Injection is especially useful.The example of moulded products include sheet material, section bar, wirebar, film, precursor, fiber, strapping,
Band, tubing, pipe, and the goods of the such as complicated shape such as machine or engine components.These moulded products are at initial formation
Afterwards can through orientation, stretching, extension, coating, anneal, paint, lamination and plating process.Because blend is thermoplastic, so system
Product can be ground and reshaping.
Temperature and can be relatively is used owing to POM compositions as herein described has the top of increase compared with pure POM
Creep is resisted and not sagging, so they can be used for making parts, as gear (is particularly useful for its middle gear frequent at a temperature of height
Be exposed to the road vehicle application of higher temperature), electronic equipment, and for wherein expectation high ductibility retain and excellent heat resistance
Those application.Other especially useful application includes the parts for conveyor system, and described conveyor system processes
Food, packed or unencapsulated absorbed product, nutrient drug food, medicine etc..
Example
Following examples further illustrate compositions as herein described and stated.
Material
POM-500: the POM resin that universal non-percussion is modified, use 2.16kg counterweight to have about when measuring at 190 DEG C
The melt flow rate (MFR) of Mn and 15g/10 minute of 30,000, with trade name500P is purchased from Du Pont.
POM-100: the POM resin that universal non-percussion is modified, use 2.16kg counterweight to have about when measuring at 190 DEG C
The melt flow rate (MFR) of Mn and 2.5g/10 minute of 65,000, with trade name100P is purchased from Du Pont.
V920: PMMA acrylic resin, use 3.8kg counterweight according to ASTM D1238 at 230 DEG C
There is during mensuration the melt flow rate (MFR) of 8.0g/10min.
E3320: polyacetals terpolymer, purchased from BASF.
Denka Boron Nitride SP-3: fine particles boron nitride, purchased from Denki Kagaku Kogyo..
1098: sterically hindered phenolic antioxidant, there is the molecular weight of 637g/ mole, purchased from Ciba.
Allantoin: there is formula C4H6N4O3, purchased from International Specialty Products, Wayne NJ.
Equipment:
Extruder for compounding: there is the 30mm co-rotating twin screw extruder of mixed zone and melting zone, be furnished with
2 hole strand die heads of 0.187 inch diameter, purchased from Coperion Corporation, Ramsey, NJ USA.
Injection: 6 ounce reciprocating screw formula injection molding unit, purchased from Nissei Corporation, Japan.
Method of testing
Relevant to imidized acrylic [IA] polymer
Employ two kinds of IA polymer under study for action, all prepare with " laboratory scale ": " peracid " IA is with " low
Acid " IA.As used herein, peracid IA has the sour percentage by weight of 5 or bigger, and low acid IA has the sour weight of 4 or less
Percentage ratio, preferably smaller than 1 percentage by weight.Following operation is for two kinds of IA of preparation:
The single screw extrusion machine using a 25mm diameter melts and initial resin metering feeding is entered 15 meters long
In the rustless steel transmission conduit of 12.5mm diameter.The polymer valve using line end regulates and controls the pressure in transmission line.
The downstream of polymer valve is the double screw extruder of a 25mm, with two vacuum discharge mouths, at pumping polymer
The amine through strand die head and removing excess before strands is cut into granule and byproduct of reaction.Use double syringe pumping system
In transmission line beginning by the injection of polymer melt of amine source.IA make and in double screw extruder remove volatile matter it
After, IA product also comprises hydroxy-acid group, anhydride group, and some unreacted esters in addition to comprising imide group.Initially
The IA of preparation could generally have 5 or the acid groups of more weight percentage ratio.The IA of " low acid " pattern is by will initially prepare
IA again sends back in extruder and adds dimethyl carbonate so that the acidic group on polymer chain is esterified and produces.
By using the screw speed of 50 revolutions per minute [rpms] on single screw extrusion machine, makeV920 with
Monomethyl amine reacts and makes IA sample, and described speed estimate divides corresponding to PMMA resin feed rate and the 43ml/ of 97g/ minute
The monomethyl amine charge velocity of clock.Oil temperature setting value for the chuck around transmission line is 280 DEG C, polymer-melt temperature reading
It it is 260 DEG C.It is emitted into the Stress control at polymer valve at 800 to 900psig (5.5 to 6.2mPa).Methyl amine injects pressure
Power is recorded as 900 to 1200psig (6.2 to 8.3mPa).In double screw extruder, the vacuum at floss hole is recorded as 17in
Hg or 58kPa.The polymer-melt temperature recorded at the granulation die head of double screw extruder is 245 DEG C.Via DSC and nitrogen
Analyze, determine that Tg is 163 DEG C and nitrogen content is 7.5 percentage by weights.The some quilts in small batches run under the conditions of same nominal
It is blended together, to provide peracid IA, such as IA-HA-1.
By again extruding the dry peracid material of preparation under above-mentioned rated condition (in 100 DEG C of setting values in dehumidifying
Dried overnight in drying machine) and prepare low acid IA (such as IA-LA-1) with dimethyl carbonate process.The screw rod of single screw extrusion machine
Rotating speed is 74rpm, estimates the feed rate corresponding to about 140g/min.Fill syringe pump by dimethyl carbonate, then with
The speed of 14ml/min injects transmission line to reduce the acid amount being present in polymer.By the oil heating of heat transfer line jacket oil
Setting value on device is set to 280 DEG C.It is 250 to 440psig (1.7 to 3mPa) that the outlet pressure of line end controls.Injection
Device pump injection pressure is 640 to 880psig (4.4 to 6mPa).Remembered at joint between single screw extrusion machine and transmission line
The melt temperature of the high acid polymer of record is 270 DEG C.At the granulation die head of double screw extruder, the melt temperature of low acid IA is 235
DEG C to 265 DEG C.Through DSC and nitrogen analysis, determine that the Tg of low acid material is 151 DEG C and nitrogen content is 7.5 percentage by weights.If will
Dry being blended together in small batches provides low acid IA.
Reanalyse the aggregation blend of each small quantities of imidized acrylic, result is summarised in lower Table A.
By use CHN analyser, Carlo Erba Model1108, through standard combustion method measure nitrogen number (as
The percentage by weight of the nitrogen of IA polymer).The imidizate percentage ratio (by weight) of polymer is calculated based on nitrogen number.Use
The nitrogen number of 100% imidizate PMMA resin prepared by monomethyl amine is 8.4.When the molecular weight in amine source rises, for 100%
The nitrogen number of imidizate declines.
Then calculated the amount of methacrylic acid by the mole of the acid neutralized by titration, so that it is determined that IA polymer
The percentage by weight of middle methacrylic acid.Can calculate with acid percentage by weight by deducting acid imide percentage by weight with 100
The percentage by weight of ester group.The amount of anhydride is assumed to ignore, owing to IR can not detect anhydride.
Measure the vitrification of IA polymer via differential scanning calorimetry [" DSC "] by ASTM D3418 (0-200 DEG C)
Transition temperature [" Tg "], wherein 0 DEG C of balance, is heated to 200 DEG C, is cooled to 0 DEG C, is then again heated to 10 DEG C/min
200 DEG C, wherein during second time heating, record Tg.
Table A
The all components of the most various samples is the most initially dry mixed, and is then fed in double screw extruder to obtain
Obtain the sample of uniform melt mixed.Specifically, 18mm Coperion double screw extruder is entered by IA sample by melt blending
This is incorporated in POM-500 or POM-100 respectively.Use two independent feeding machines, at rear-fed IA and the POM of extruder
Composition.Before Gong Huning, at 100 DEG C, it is dried IA granule five hours.The most potent screw design is used for providing required shearing
And combined amount.After leaving extruder die head, the quencher in a water bath of strands the most out, then cut with conventional line material cutter
It is slit into the granule of 3mm length.Then make granule dried overnight at 80 DEG C, be molded on 1.5 ounces of Arburg injection machines subsequently
Thus form test bar.
Compounding and injection moulding process are smooth and easy and have no problem, and the test bar being simply made up of pure IA polymer is the easiest
Broken.
Utilize ASTM Test Method to carry out mechanical test and Thermal test.Bending modulus is measured according to ASTM D-790.Root
Izod notched impact strength is measured according to ASTM D-256.At 23 DEG C, simple beam impact strength is measured according to ISO179.According to
ASTM D1525 measures softening temperature, and wherein temperature increase rate is 2.0 DEG C/min, applies the infiltration of 10 Newton force and 1mm.
Under 264psi (1.8MPa), heat deflection temperature (HDT) is measured according to ASTM D-648.Carry out dynamic mechanical analysis (DMA) to comment
Estimate modulus at a temperature of rising to increase, and during constant rigidity, top uses the increase of temperature.
Table 1 shows the heat deflection temperature of the blend of POM-500 and peracid IA and low acid IA.
Table 1
Compared with pure POM-500, POM-500 uses the IA-HA-1 (peracid) (comparative example C2) of 5 percentage by weights
Time, HDT reduces to a certain extent.When being mixed with low acid IA-LA-1, HDT increases, but simply increases slightly.
Table 2 shows various POM-100 blend and the heat deflection temperature of various IA.Owing to IA-LA-1 is extremely fragile, it is impossible to
Make the test board for HDT test, so Tg based on IA-LA-1 estimates its HDT.
Table 2
The least improvement (comparative example C5 is only shown with the HDT of POM-100 modified for the peracid IA-HA-2 of 5 percentage by weights
Compared with comparative example C3).But, for using the example of at most 5 percentage by weights low acid IA-LA-1, HDT significantly increases.With
Pure POM compositions is compared, along with low acid IA is loaded onto about 8 percentage by weights (combination meter based on POM Yu IA), HDT from about 1
About 35% is increased to from about 5%.
As table 2 collects, the low acid IA of only 2.5 percentage by weights and 5 percentage by weights is blended, makes check sample respectively
HDT increases to 124 DEG C and 128 DEG C from 97.6 DEG C；Increase by 26 DEG C and 31 DEG C i.e., respectively, or 27% and 31%.Up to about 8 weight
The example of the low acid IA of percentage ratio is displayed without extra improvement.
When the similar increase observing HDT when loading and use IA-LA-2 with 5 percentage by weights.Use the one of IA-LA-3
Series sample shows, realizes the maximum increase of HDT between the IA of 5 and 10 percentage by weights loads.The amount of use IA-LA-3 is
The HDT of the sample of 10 to 40 percentage by weights is substantially identical (comparative example C6-C10).Imido weight in IA-LA-3
Percentage ratio is less than imido percentage by weight in IA-LA-1, and its Tg is as the same.Without being bound to any particular theory, these because of
It is relatively low that element may be interpreted as the HDT what observes when the IA-LA-3 of 5 percentage by weight loading capacities.
In general, the result in table 2 is shown, owing to only combining IA in a small amount, and the lowest acid IA, described herein
The thermostability of POM compositions has unexpected and surprising improvement.IA for about 1 to about 40 percentage by weight loads
HDT increases；But the loading effect for 1 to 8 percentage by weight is the most obvious, especially about 2 to about 5 percentage by weights.Pass through
It is not particularly significant that the HDT adding the IA of about 8 to about 40 percentage by weights and realize increases.Exceeding about 40 percentage by weights
IA, and particularly when the IA of 50 to 100 percentage by weights, the continuous phase in blend is likely become IA from POM, and this continues
And the key property of blend will be changed.Specifically, when blend becomes to have more IA, HDT increases the most again
It is up to the HDT of pure IA.Acid content exceedes the IA sample of about 2 percentage by weights than 5 weight percent content display much less
HDT increases.
The comparison of example 1 and example 5 shows, adds low acid IA and be not result in as to height in low-molecular-weight POM-500
The most significantly improve when molecular weight POM-100 adds similar low acid IA.
Along with about 1 percentage by weight also increases to the interpolation of about 8 percentage by weights, the rigidity of POM-100.Table 3 and table 4 show
Show, for the bending modulus (under big strain) under the IA in 2.5 to 7.5 weight percentage ranges, room temperature and secant modulus (
Under small strain) all increase about 30 percentage ratios.When exceeding the IA of about 8 percentage by weights to about 40 percentage by weights, bending modulus has
The least extra improvement.
Table 3
Table 4
Add IA hot strength without adverse affects.On the contrary, table 5 illustrates, the IA of at most 5 percentage by weights makes hot strength
Slightly increase.Although the elongation that table 5 shows low amounts reduces, but result shows, sample still keeps preferable ductility to meet
Final use demand.Specifically, there is the sample of 20 percentage by weights or bigger percentage by weight IA at these tension tests
In be displayed without surrender, there is the breaking strain being substantially reduced.
Table 5
* not fracture tensile strength (not observing surrender)
Dynamic mechanical analysis (DMA) result display storage modulus significantly increases (rigidity).Storage modulus E ' represent material
The component of elasticity of modulus, as relative with viscous components.Table 6 shows example 5, for 70 DEG C, 80 DEG C, 90 DEG C and the temperature of 100 DEG C
Scope, and use the IA of 5 percentage by weights, at a temperature of identical test, the increase scope of storage modulus is tester
24 percentage ratios are to 34 percentage ratios.There are 5 to 8 weight hundred and demonstrate the least extra improvement than the sample of IA scope.
Table 6
Table 7 shows, blend modified for IA is compared with glass reinforced POM-100 (C11): (1) elongation keeps；
And (2) minimizing of Charpy Impact is the least.
Table 7
Table 8 shows, in applying 2MPa power runs the long term high temperature creep test of 60 minutes at 90 DEG C, with unmodified
POM compares, and the POM compositions comprising the POM-100 modified with 2.5 and 5 percentage by weight IA experienced by about 20 percentage by weights
Creep reduce.
Table 8
Table 9 describes the thermogravimetric analysis to test sample [" TGA "] and demonstrates that comprising IA in POM compositions described herein leads
The heat stability causing them improves.In nitrogen atmosphere, molding test sample rod is added from 30 DEG C with the speed of 10 DEG C/min
Heat, to 230 DEG C, then keeps 60 minutes at 230 DEG C.Escaping gas during temperature ramp rises is detected with infrared spectrum.Receive
Collect and analyze escaping gas material, the formaldehyde of effusion during whole heating.Table 9 shows TGA result, with pure POM
Comparing, the total weight loss of sample is relatively low and formaldehyde effusion is less.
Table 9
Table 10 illustrates the test result of the creep resistance improvement for other POM compositions described herein.Creep resistance
For the equivalent terms to the X% creep strain time.In table 10, all components of sample is the most initially dry mixed, and then feeds
Enter in double screw extruder to obtain the sample of improving uniformity of melt mixing.Use 200 DEG C to 210 DEG C roller temperature and with
The throughput of the 30lb/hr of 150rpm is compounded compositions.The quencher in the water-bath of 25 DEG C of the melt extrudate of gained, then makes
Grain becomes about 0.25in [1cm] long and the cylindrical particle of 0.125in [0.5cm] diameter.Then make granule in vacuum at 80 DEG C
Under be dried 4hr.
After being dried, granule feeding is entered in injection molding unit, its cylinder is heated to 200 DEG C to 210 DEG C.Mould is heated
To 90 DEG C.Use the injection mould of shape described in ISO527-2/1A.Before test, make gained specimen at 23 DEG C, 50% phase
To wetting balance 48hr.
Tensile creep test is carried out according to ISO899-1.Tensile creep test is entered under the primary stress of 90 DEG C and 25MPa
OK.Extension meter is used to measure the elongation strain of sample.All sample standard deviations are tensioned to about 10% elongation strain.
In table 10, C-12, C-13 and C-14 are comparative example, and example 8 and example 9 are POM compositions described herein
Example.Table 10 shows, uses the creep resistance of the example 8 of 2.5 percentage by weights low acid IA to experienced by the increasing of significant 208%
(being reported as the time to 5% creep strain) greatly herein, exceeded the increase of the creep resistance of C-14, C-14 is containing 0.1 weight
Measure percentage ratio boron nitride SP-3 and pbz polymer amount POM of 0.05 percentage by weight allantoin but do not contain the POM compositions of IA.Tool
The result of body is: 720 seconds (for C-14) compares 2220 seconds (for example 8).Use the example 9 of the 5 low IA of percentage by weight
Creep resistance shows the increase of the most significant 300%, the increase of the creep resistance more than C-14.It is essential that C-14
By three comparisons being tested have the comparative example of high creep resistance, it is likely that be because with the addition of boron nitride and allantois
The reason of element.Therefore, with compareing of C-14, example 8 and example 9 demonstrate that the minimum of creep resistance improves.
Say in a capsule, the increase compareing display 1750% of the time to 5% creep strain of example 8 and C-12, i.e.
The increase represented with the second of 120 to 2220.Relative to C-12, the time to 5% creep of example 9 experienced by the increasing of 2450%
Add, i.e. the increase represented with the second of 120 to 3060.
Example 8 has obtained similar surprising result with example 9 with the comparison of the time to 5% creep strain of C-13.C-
13 comprise 2 percentage by weights3320, it is reported as the HDT with 105 DEG C, is likely to improve compared with C-12
Its creep resistance.Example 8 has the increase of 240 to 2220 seconds represented with the second, the increase of 825%.Example 9 has with stopwatch
The increase of 240 to 3060 seconds shown, the increase of 1175%.
Creep resistance also can be measured as the time to 7% creep strain.When using that measurement of creep resistance,
Example 8 and the example 9 raising relative to C-12 are respectively 1463% and 2000%.Relative to C-13, example 8 and example 9 extremely
The increase of the time of 7% creep strain is respectively 681% and 950%.Relative to C-14, example 8 and example 9 to 7% creep
The increase of the time of strain is respectively 191% and 291%.
Table 10
Claims (11)
1. the method increasing heat deflection temperature, comprising:
Melting mixing
The imidized acrylic of (a) 1 to 8 percentage by weight,
It has
Acid content and
Imidizate degree, and
Obtain by processing acrylic polymer by the monoalkylamine with monoalkyl；
B the number-average molecular weight of () 92 to 99 percentage by weight is 50, the polyformaldehyde of 000 to 250,000g/mol, and
(c) optionally, one or more other additives,
To obtain the compositions of melting mixing,
Wherein:
A the percentage by weight of () and (b) is each based on the combined wt meter of (a) and (b),
Described monoalkyl has one to five carbon atom,
Described imidizate degree is 20% to 100%,
Described acid content is 0 to 2 percentage by weight of described imidized acrylic；And
As measured under the primary stress of 90 DEG C and 25MPa by ISO899-1, the compositions of described melting mixing to 5% compacted
The time that allergic effect becomes is 200% or bigger of the same combination without (a).
Method the most according to claim 1, wherein as measured at 1.8MPa by ISO 75-1/-2, heat deflection temperature
It is increased to 20% or bigger of the same combination without (a).
Method the most according to claim 1 and 2, wherein said imidized acrylic comprises cyclic imide list
Unit.
Method the most according to claim 1 and 2, wherein said imidized acrylic is with 1 to 5 percentage by weight
Amount be present in the compositions of described melting mixing.
Method the most according to claim 1 and 2, wherein said imidized acrylic is by processing choosing with methylamine
Obtain from following acrylic polymer:
Poly-(methyl methacrylate)；Poly-(acrylic acid methyl ester .)；Acrylic acid methyl ester. with at least one other selected from styrene, third
The copolymer of the comonomer of alkene nitrile, vinyl acetate, ethylene, butadiene or methyl vinyl ether；And methyl methacrylate
Being total to selected from styrene, acrylonitrile, vinyl acetate, ethylene, butadiene or methyl vinyl ether that ester is other with at least one
The copolymer of poly-monomer.
Method the most according to claim 5, wherein said acrylic polymer is poly-(methyl methacrylate).
Method the most according to claim 1 and 2, wherein said polyformaldehyde has 50, and the number of 000 to 80,000g/mol is equal
Molecular weight.
Method the most according to claim 1 and 2, wherein said polyformaldehyde is selected from homopolymer, copolymer, and these is mixed
Compound.
Method the most according to claim 1 and 2, wherein said imidizate degree is 60% to 100%.
Method the most according to claim 1 and 2, wherein said imidizate degree is 80% to 100%.
11. methods according to claim 1 and 2, wherein said imidizate degree is 90% to 100%.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/306806 | 2011-11-29 | ||
| US13/306,806 US20130137811A1 (en) | 2011-11-29 | 2011-11-29 | Modifying Polyoxymethylene Imidized Acrylic Resins |
| US13/306757 | 2011-11-29 | ||
| US13/306,757 US8445089B1 (en) | 2011-11-29 | 2011-11-29 | Polyoxymethylene modified with imidized acrylic resins |
| PCT/US2012/063921 WO2013081785A1 (en) | 2011-11-29 | 2012-11-07 | Modifying polyoxymethylene with imidized acrylic resins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104254550A CN104254550A (en) | 2014-12-31 |
| CN104254550B true CN104254550B (en) | 2016-11-30 |
Family
ID=
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874817A (en) * | 1982-05-07 | 1989-10-17 | E. I. Du Pont De Nemours And Company | Compositions of imidized acrylic polymers and polyamides |
| US5264483A (en) * | 1985-08-27 | 1993-11-23 | Rohm And Haas Company | Imide polymers |
| US5318813A (en) * | 1989-10-12 | 1994-06-07 | E. I. Du Pont De Nemours And Company | Polyoxymethylene/thermoplastic polyurethane/amorphous thermoplastic polymer blends |
| CN1788052A (en) * | 2003-05-13 | 2006-06-14 | 纳幕尔杜邦公司 | Modified polyacetals for decorative applications |
| CN1863863A (en) * | 2003-10-17 | 2006-11-15 | 罗姆两合公司 | Polymer mixture for injection mouldings with a matt surface |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4874817A (en) * | 1982-05-07 | 1989-10-17 | E. I. Du Pont De Nemours And Company | Compositions of imidized acrylic polymers and polyamides |
| US5264483A (en) * | 1985-08-27 | 1993-11-23 | Rohm And Haas Company | Imide polymers |
| US5318813A (en) * | 1989-10-12 | 1994-06-07 | E. I. Du Pont De Nemours And Company | Polyoxymethylene/thermoplastic polyurethane/amorphous thermoplastic polymer blends |
| CN1788052A (en) * | 2003-05-13 | 2006-06-14 | 纳幕尔杜邦公司 | Modified polyacetals for decorative applications |
| CN1863863A (en) * | 2003-10-17 | 2006-11-15 | 罗姆两合公司 | Polymer mixture for injection mouldings with a matt surface |
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