NO139958B - MOMOMER EMULSION STABILIZER. - Google Patents
MOMOMER EMULSION STABILIZER. Download PDFInfo
- Publication number
- NO139958B NO139958B NO394470A NO394470A NO139958B NO 139958 B NO139958 B NO 139958B NO 394470 A NO394470 A NO 394470A NO 394470 A NO394470 A NO 394470A NO 139958 B NO139958 B NO 139958B
- Authority
- NO
- Norway
- Prior art keywords
- oxymethylene
- weight
- polymer
- units
- polymers
- Prior art date
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- 239000003381 stabilizer Substances 0.000 title description 16
- 239000000839 emulsion Substances 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims description 78
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 claims description 60
- -1 alkylene bisphenol Chemical compound 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 150000002462 imidazolines Chemical class 0.000 claims description 3
- 239000003017 thermal stabilizer Substances 0.000 claims description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 13
- 150000004292 cyclic ethers Chemical class 0.000 description 12
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 11
- 238000005979 thermal decomposition reaction Methods 0.000 description 11
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 10
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 229910015900 BF3 Inorganic materials 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- ROHTVIURAJBDES-UHFFFAOYSA-N 2-n,2-n-bis(prop-2-enyl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(CC=C)CC=C)=N1 ROHTVIURAJBDES-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000018102 proteins Nutrition 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WGTDLPBPQKAPMN-MDZDMXLPSA-N 2-[2-[(e)-heptadec-8-enyl]-4,5-dihydroimidazol-1-yl]ethanol Chemical compound CCCCCCCC\C=C\CCCCCCCC1=NCCN1CCO WGTDLPBPQKAPMN-MDZDMXLPSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- ULAGGPJVDRGWTI-UHFFFAOYSA-N 1,3,5-trioxepane Chemical compound C1COCOCO1 ULAGGPJVDRGWTI-UHFFFAOYSA-N 0.000 description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 2
- BGCSUUSPRCDKBQ-UHFFFAOYSA-N 2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OCOCC21COCOC2 BGCSUUSPRCDKBQ-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 description 2
- WUIIRPAMGBRKCV-UHFFFAOYSA-N n-ethenyl-n-phenylacetamide Chemical class CC(=O)N(C=C)C1=CC=CC=C1 WUIIRPAMGBRKCV-UHFFFAOYSA-N 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229960002446 octanoic acid Drugs 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 2
- 229960003868 paraldehyde Drugs 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- CXCSZVYZVSDARW-UHFFFAOYSA-N 1,2-dicyanoguanidine Chemical compound N#CNC(N)=NC#N CXCSZVYZVSDARW-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- IIXXKZSXDZZOBL-UHFFFAOYSA-N 1-cyano-2-(2-hydroxyethyl)guanidine Chemical compound N#C\N=C(/N)NCCO IIXXKZSXDZZOBL-UHFFFAOYSA-N 0.000 description 1
- XFIZJENETBUYNB-UHFFFAOYSA-N 1-cyano-2-(hydroxymethyl)guanidine Chemical compound N#CNC(N)=NCO XFIZJENETBUYNB-UHFFFAOYSA-N 0.000 description 1
- IKKZUUMAGYBBFE-UHFFFAOYSA-N 1-cyano-2-ethylguanidine Chemical compound CCNC(N)=NC#N IKKZUUMAGYBBFE-UHFFFAOYSA-N 0.000 description 1
- SIQWQBQGWREFSE-UHFFFAOYSA-N 1-cyano-2-methylguanidine Chemical compound CNC(N)=NC#N SIQWQBQGWREFSE-UHFFFAOYSA-N 0.000 description 1
- SRUGWSFEPMKUAK-UHFFFAOYSA-N 1-cyano-2-propan-2-ylguanidine Chemical compound CC(C)NC(N)=NC#N SRUGWSFEPMKUAK-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical class C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical class C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 description 1
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- KLGKVMMWRDYKJM-UHFFFAOYSA-N 2,2-dimethylcyclobutane-1,3-dicarboxylic acid Chemical compound CC1(C)C(C(O)=O)CC1C(O)=O KLGKVMMWRDYKJM-UHFFFAOYSA-N 0.000 description 1
- QNDGQRJVVZJMJO-UHFFFAOYSA-N 2-(2-undecyl-4,5-dihydroimidazol-1-yl)ethanol Chemical compound CCCCCCCCCCCC1=NCCN1CCO QNDGQRJVVZJMJO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XKDKGANKVZRJMR-UHFFFAOYSA-N 2-n,2-n-diphenyl-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(C=2C=CC=CC=2)C=2C=CC=CC=2)=N1 XKDKGANKVZRJMR-UHFFFAOYSA-N 0.000 description 1
- LGEXGKUJMFHVSY-UHFFFAOYSA-N 2-n,4-n,6-n-trimethyl-1,3,5-triazine-2,4,6-triamine Chemical compound CNC1=NC(NC)=NC(NC)=N1 LGEXGKUJMFHVSY-UHFFFAOYSA-N 0.000 description 1
- GGHBKCSNURXPNB-UHFFFAOYSA-N 2-n,4-n,6-n-triphenyl-1,3,5-triazine-2,4,6-triamine Chemical compound N=1C(NC=2C=CC=CC=2)=NC(NC=2C=CC=CC=2)=NC=1NC1=CC=CC=C1 GGHBKCSNURXPNB-UHFFFAOYSA-N 0.000 description 1
- CVKGSDYWCFQOKU-UHFFFAOYSA-N 2-n-butyl-1,3,5-triazine-2,4,6-triamine Chemical compound CCCCNC1=NC(N)=NC(N)=N1 CVKGSDYWCFQOKU-UHFFFAOYSA-N 0.000 description 1
- JIHOVGXINXMLLR-UHFFFAOYSA-N 2-n-phenyl-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2C=CC=CC=2)=N1 JIHOVGXINXMLLR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NFBVOAPHAOKEGN-UHFFFAOYSA-N 3,3,4,4-tetrapropyloxolane-2,5-dione Chemical compound CCCC1(CCC)C(=O)OC(=O)C1(CCC)CCC NFBVOAPHAOKEGN-UHFFFAOYSA-N 0.000 description 1
- LEVONNIFUFSRKZ-UHFFFAOYSA-N 3-(carboxymethyl)-2,2-dimethylcyclobutane-1-carboxylic acid Chemical compound CC1(C)C(CC(O)=O)CC1C(O)=O LEVONNIFUFSRKZ-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- BCERVBGVOSICNO-UHFFFAOYSA-N 3-[2-(2-carboxyethyl)phenyl]propanoic acid Chemical class OC(=O)CCC1=CC=CC=C1CCC(O)=O BCERVBGVOSICNO-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- DFATXMYLKPCSCX-UHFFFAOYSA-N 3-methylsuccinic anhydride Chemical compound CC1CC(=O)OC1=O DFATXMYLKPCSCX-UHFFFAOYSA-N 0.000 description 1
- IUDNGVFSUHFMCF-UHFFFAOYSA-N 4-(chloromethyl)-1,3-dioxolane Chemical compound ClCC1COCO1 IUDNGVFSUHFMCF-UHFFFAOYSA-N 0.000 description 1
- FQTWXIRTTKHYSK-UHFFFAOYSA-N 4-[2-(3-carboxypropyl)phenyl]butanoic acid Chemical class OC(=O)CCCC1=CC=CC=C1CCCC(O)=O FQTWXIRTTKHYSK-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- YZVJFFKAKLWXOE-UHFFFAOYSA-N 6-heptadecyl-1,3,5-triazine-2,4-diamine Chemical compound CCCCCCCCCCCCCCCCCC1=NC(N)=NC(N)=N1 YZVJFFKAKLWXOE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- 102000011632 Caseins Human genes 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 102000006395 Globulins Human genes 0.000 description 1
- 108010044091 Globulins Proteins 0.000 description 1
- 108010068370 Glutens Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920009382 Polyoxymethylene Homopolymer Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000000320 amidine group Chemical group 0.000 description 1
- YSKUZVBSHIWEFK-UHFFFAOYSA-N ammelide Chemical compound NC1=NC(O)=NC(O)=N1 YSKUZVBSHIWEFK-UHFFFAOYSA-N 0.000 description 1
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- GEHJBWKLJVFKPS-UHFFFAOYSA-N bromochloroacetic acid Chemical compound OC(=O)C(Cl)Br GEHJBWKLJVFKPS-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- STZUMARNGFQGPH-UHFFFAOYSA-N chloromethoxyethene Chemical group ClCOC=C STZUMARNGFQGPH-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000001993 dienes Chemical group 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000035929 gnawing Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical group C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000003951 lactams Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical class N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical class C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Fremgangsmåte til å øke den termiske stabilitet hos oksymetylenpolymerer. Process for increasing the thermal stability of oxymethylene polymers.
Denne oppfinnelse vedrører oksymetylenpolymerer som kan formes under varme This invention relates to oxymethylene polymers which can be formed under heat
og trykk og befatter seg særlig med å forbedre deres varmestabilitet. and pressure and is particularly concerned with improving their thermal stability.
Oksymetylenpolymerer er polymerer Oxymethylene polymers are polymers
med stadig tilbakevendende -CH.O-enheter. Polymerer som består så å si ute-lukkende av -CH,0-enheter kan fremstilles ved polymerisering av vannfritt formaldehyd eller ved polymerisering av trioksan, den sykliske trimer av formaldehyd. with constantly recurring -CH.O units. Polymers which consist, so to speak, exclusively of -CH,0 units can be produced by polymerization of anhydrous formaldehyde or by polymerization of trioxane, the cyclic trimer of formaldehyde.
Polymerer kan også oppnåes hvor det in-neholdes andre enheter i tillegg til -CH.,0-enhetene, idet de mest verdifulle produk-ter er de hvori -CH.jO-enhetene danner hovedandelen av de enheter som er tilstede i polymermolekylene. Slike polymerer kan fåes ved sampolymerisering av trioksan med egnete monomerer. Polymers can also be obtained which contain other units in addition to the -CH.,0 units, the most valuable products being those in which the -CH.jO units form the majority of the units present in the polymer molecules. Such polymers can be obtained by copolymerizing trioxane with suitable monomers.
Således kan det oppnåes polymerer som Thus, polymers can be obtained which
inneholder både -CHaO-enheter og andre contains both -CHaO units and others
enheter ved å sampolymerisere trioksan units by copolymerizing trioxane
med et syklisk anhydrid, for eksempel ravsyreanhydrid, n-dodecenyl-ravsyreanhydrid, maleinsyreanhydrid, ftalsyreanhy-drid, heksahydroftalsyreanhydrid, itacon-syreanhydrid, metyl-ravsyreanhydrid, with a cyclic anhydride, for example succinic anhydride, n-dodecenyl succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, methyl succinic anhydride,
tetrapropyl-ravsyreanhydrid, 1,4,5,6,7,7-heksa-klor-bicyclo-(2,2,1)-5-hepten-2,3-anhydrid, metylnadinsyreanhydrid og polymerer av anhydrider som ineholder an-hydridstrukturen såsom sampolymeren av tetrapropyl succinic anhydride, 1,4,5,6,7,7-hexa-chloro-bicyclo-(2,2,1)-5-heptene-2,3-anhydride, methylnadic anhydride and polymers of anhydrides containing the anhydride structure such as the copolymer of
vinylacetat og maleinsyreanhydrid og ho-mopolymerene av akrylsyreanhydrid. Sampolymerer av trioksan med slike sykliske vinyl acetate and maleic anhydride and the homopolymers of acrylic anhydride. Copolymers of trioxane with such cyclic
anhydrider inneholder både -CH„0-enheter og -CO-R-CO-O-enheter; der hvor anhydrides contain both -CH„0 units and -CO-R-CO-O units; where
sampolymerisatet av monomeren er en the copolymer of the monomer is a
polymer av et anhydrid, er sampolymeri- polymer of an anhydride, is copolymeri-
seringen med trioksan i realiteten en tverr-bindingsoperasjon og det er ønskelig at den blir gjennomført mens reaksjonsmas-sen har den ønskete form, for eksempel i en lukket form. Et tverravbundet produkt kan også fåes med et monomerisk umettet syklisk anhydrid såsom maleinsyreanhydrid ved å oppvarme sampolymeren ale-ne, eller i nærvær av en etylenisk umettet sampolymer, for eksempel styren. the serination with trioxane is in reality a cross-linking operation and it is desirable that it is carried out while the reaction mass has the desired shape, for example in a closed form. A cross-linked product can also be obtained with a monomeric unsaturated cyclic anhydride such as maleic anhydride by heating the copolymer alone, or in the presence of an ethylenically unsaturated copolymer, for example styrene.
Dessuten kan trioksan sampolymeres med epiklorhydrin eller med 4-klormetyl-1,3-dioksolan for å oppnå polymerer som inneholder -CH,0-enheter og 2-klormetyl-oksyetylenenheter. Disse klorholdige sam-monomerer er tilbøyelige til å reagere hef-tig med seg selv, så at det er ønskelig å tilsette iallfall endel av sammonomeren etter at polymeriseringen har startet. Also, trioxane can be copolymerized with epichlorohydrin or with 4-chloromethyl-1,3-dioxolane to obtain polymers containing -CH,0 units and 2-chloromethyloxyethylene units. These chlorine-containing comonomers tend to react violently with themselves, so that it is desirable to add at least part of the comonomer after the polymerization has started.
Polymerer som inneholder både -CH .O-grupper og betaoksypropylengrupper med en gammaetersubstituent kan oppnåes ved å sampolymerisere trioksan med en glycidyleter, for eksempel med metyl-, etyl-, propyl-, cyclo-heksyl-, isopropyl-, n-butyl-, isobutyl-, t-butyl-, allyl- eller fenylglyci-dyleter eller med diglysidyleter eller bis-fenol A (di-p-fenylolpropan). Polymers containing both -CH .O groups and betaoxypropylene groups with a gamma ether substituent can be obtained by copolymerizing trioxane with a glycidyl ether, for example with methyl, ethyl, propyl, cyclohexyl, isopropyl, n-butyl, isobutyl, t-butyl, allyl or phenylglycidyl ether or with diglycidyl ether or bis-phenol A (di-p-phenylolpropane).
De viktigste polymerer er kanskje de som inneholder både -CH.O-enheter og oksyalkylenenheter med direkte bundne kullstoffatomer, særlig oksyetylenenheter. Slike polymerer kan oppnåes ved å sampolymerisere trioksan med en syklisk eter såsom etylenoksyd, 1,3-dioksolan, 1,3,5-trioksepan, 1,3-dioksan, trimetylenoksyd, pentametylenoksyd, 1,2-propylenoksyd, 1,2-butylenoksyd, neopentylformal, pentaery-tritoldiformal, paraldehyd, tetrahydrofu-ran og butadienmonoksyd. Disse sampoly-; merer er kjennetegnet ved en merkbart j større termisk stabilitet enn oksymetylen-homopolymerer. The most important polymers are perhaps those containing both -CH.O units and oxyalkylene units with directly attached carbon atoms, especially oxyethylene units. Such polymers can be obtained by copolymerizing trioxane with a cyclic ether such as ethylene oxide, 1,3-dioxolane, 1,3,5-trioxepane, 1,3-dioxane, trimethylene oxide, pentamethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide , neopentyl formal, pentaerythritol diformal, paraldehyde, tetrahydrofuran and butadiene monoxide. These copoly-; more are characterized by a noticeably greater thermal stability than oxymethylene homopolymers.
For formålene ifølge den foreliggende oppfinnelse innbefatter uttrykket oksymetylenpolymerer alle slike polymerer, hva enten de består helt av -CH20-enheter eller-i deres struktur innbefatter andre enheter slik som beskrevet foran, og inkluderer også ter-polymerer av trioksan med flere enn en sammonomer, for eksempel sampolymer av trioksan, en syklisk eter og en glycidyleter eller epiklorhydrin. Alle oksy-metylenpolymerene varierer i termisk stabilitet og molekylarvekt alt etter den fremgangsmåte hvoretter de er fremstillet. Men selv de kjente polymerer av høyest termisk stabilitet lar litt tilbake å ønske når det gjelder dette trekk, og den foreliggende oppfinnelse befatter seg med å forbedre den termiske stabilitet for oksymetylenpolymerer ved hjelp av visse nye stabilisatorer. For the purposes of the present invention, the term oxymethylene polymers includes all such polymers, whether they consist entirely of -CH 2 O units or-in their structure include other units as described above, and also includes ter-polymers of trioxane with more than one comonomer, for example copolymer of trioxane, a cyclic ether and a glycidyl ether or epichlorohydrin. All the oxy-methylene polymers vary in thermal stability and molecular weight according to the process by which they are produced. However, even the known polymers of the highest thermal stability leave something to be desired in this respect, and the present invention is concerned with improving the thermal stability of oxymethylene polymers by means of certain novel stabilizers.
Ifølge den foreliggende oppfinnelse forbedres varmestabiliteten for oksymetylenpolymerer ved å blande inn i dem en amidinforbindelse, det vil si en forbindelse med et kullstoffatom i dobbelt binding til et nitrogenantom og i enkel binding til et annet. En meget effektiv klasse av amidinforbindelser er de N-substituerte amidinforbindelser hvori et annet nitrogenatom har en enkel binding til amidingruppen, fortrinsvis ved kullstoffatomet. According to the present invention, the thermal stability of oxymethylene polymers is improved by mixing into them an amidine compound, that is to say a compound with a carbon atom in a double bond to a nitrogen atom and in a single bond to another. A very effective class of amidine compounds are the N-substituted amidine compounds in which another nitrogen atom has a single bond to the amidine group, preferably at the carbon atom.
Slike amidinforbindelser innbefatter cyanoguanidin og andre forbindelser som inneholder det divalente radikal: N=C-NH-C(NH)-N=. Blant de egnete substituerte cyanoguanidiner som kan anvendes er dem som har en eller to substituenter ved 3-nitrogenposisjonen i guanidinkjer-nen, innbefattet alkyl-, aryl-, cyclo-alkyl-, hydroksyalkyl-, haloalkyl-, haloaryl og andre substituenter. Spesielle forbindelser som er egnet innbefatter l-cyano-3-me-tylguanidin, l-cyano-3-etylguanidin, 1-cy-ano-3-isopropylguanidin, l-cyano-3,3-dife-nylguanidin, l-cyano-3-hydroksymetylgua-nidin, l-cyano-3-dodecylguanidin, 1-cy-ano-3- (2-hydroksyetyl) -guanidin, 1-cyano-3- (2-brometyl) -guanidin, l-cyano-3- (m-klorfenyl)-guanidin og 1,3-dicyanoguani-din. Such amidine compounds include cyanoguanidine and other compounds containing the divalent radical: N=C-NH-C(NH)-N=. Among the suitable substituted cyanoguanidines which can be used are those which have one or two substituents at the 3-nitrogen position in the guanidine nucleus, including alkyl, aryl, cycloalkyl, hydroxyalkyl, haloalkyl, haloaryl and other substituents. Particular compounds which are suitable include 1-cyano-3-methylguanidine, 1-cyano-3-ethylguanidine, 1-cyano-3-isopropylguanidine, 1-cyano-3,3-dife-nylguanidine, 1-cyano- 3-hydroxymethylguanidine, l-cyano-3-dodecylguanidine, 1-cyano-3-(2-hydroxyethyl)-guanidine, 1-cyano-3-(2-bromomethyl)-guanidine, l-cyano-3- (m-chlorophenyl)-guanidine and 1,3-dicyanoguanidine.
Polyaminotriazoler omfatter en annen egnet klasse av amidinforbindelser. Polyaminotriazoler kan fremstilles ved å oppvarme en blanding av et dihydrazid av en dikarboksylsyre med vandig hydrazinhyd-rat. For et spesielt dihydrazid vil produk-tets molekyl vekt avhenge av reaksjonstem-peraturen, mengden av vann og reaksjo-nens varighet. Høyere temperaturer, lavere andeler vann og lengere reaksjonstider vil gjerne lede til høyere molekyl vekt. Polyaminotriazoles comprise another suitable class of amidine compounds. Polyaminotriazoles can be prepared by heating a mixture of a dihydrazide of a dicarboxylic acid with aqueous hydrazine hydrate. For a particular dihydrazide, the molecular weight of the product will depend on the reaction temperature, the amount of water and the duration of the reaction. Higher temperatures, lower proportions of water and longer reaction times will tend to lead to higher molecular weight.
Den foretrukne klasse av polyaminotriazoler er den som har strukturenheter av formelen: The preferred class of polyaminotriazoles are those having structural units of the formula:
hvori R er en alkylengruppe med fra 6 til 12 kullstoffatomer. De fremstilles som beskrevet foran under anvendelse av dihydra-zidene av dialkanolsyrer med fra 8 til 14 wherein R is an alkylene group having from 6 to 12 carbon atoms. They are prepared as described above using the dihydrazides of dialkanolic acids with from 8 to 14
kullstoffatomer som reaksjonsdeltakere. carbon atoms as reaction participants.
Blant de foretrukne dihydrazider er iso-sebacin-dihydrazid, sebacin-dihydrazid, Among the preferred dihydrazides are iso-sebacin dihydrazide, sebacin dihydrazide,
azelain-dihydrazid, suberindihydrazid, adi-pindihydrazid, metyladipindihydrazid, de-candionsyre-undecandion-dihydrazid. azelain dihydrazide, suberindihydrazide, adipindihydrazide, methyladipindihydrazide, decanedionic acid undecandione dihydrazide.
Man kan også anvende polyaminotriazoler som inneholder strukturenheter av den foranstående formel hvori R er et di-valent organisk radikal (fritt for reaktive grupper) andre enn en alkylengruppe med fra 6 til 12 kullstoffatomer, for eksempel polyaminotriazoler fremstillet fra dihydra-zidene av syrer, såsom de følgende: You can also use polyaminotriazoles containing structural units of the above formula in which R is a divalent organic radical (free of reactive groups) other than an alkylene group with from 6 to 12 carbon atoms, for example polyaminotriazoles prepared from the dihydrazides of acids, such as the following:
Isoftalsyre. Isophthalic acid.
Tereftalsyre. Terephthalic acid.
Fenylendieddiksyrer. Fenylendipropionsyrer. Fenylendibutyrinsyrer. p,p'-dikarboksy-l,5-difenoksypentan. p,p'-dikarboksy-l,4-difenoksybutan. p,p'-dikarboksy-difenoksymetan. p-karboksy-5-fenoksymetyl-pyromusin-syre. Phenylene acetic acids. Phenylene dipropionic acids. Phenylenedibutyric acids. p,p'-dicarboxy-1,5-diphenoxypentane. p,p'-dicarboxy-1,4-diphenoxybutane. p,p'-dicarboxydiphenoxymethane. p-Carboxy-5-phenoxymethyl-pyromucic acid.
Tio-bis-cenantinsyre. Tio-bis-kaprylsyre. Sulfon-bis-kaprylsyre. Tio-bis-valeriansyre. Sulfon-bis-propionsyre. Tio-bis-butyrinsyre. Sulfon-bis-butyrinsyre. Tio-bis-eddiksyre. Sulfon-bis-eddiksyre. p,p'-dikarboksydifenyl-l,4-dikarboksy-naftalin. Thio-bis-cenanthic acid. Thio-bis-caprylic acid. Sulfon-bis-caprylic acid. Thio-bis-valeric acid. Sulphonic bis-propionic acid. Thio-bis-butyric acid. Sulfon-bis-butyric acid. Thio-bis-acetic acid. Sulphonic bis-acetic acid. p,p'-dicarboxydiphenyl-1,4-dicarboxynaphthalene.
Pininsyre. Pinic acid.
Norpininsyre. Norpinic acid.
Homopininsyre. Homopinic acid.
Polyaminotriazoler for anvendelse i samsvar med denne oppfinnelse har for-trinnsvis en spesifikk viskositet på minst 0,3, for eksempel fra 0,3 til 0,7, i 0,1 vektsprosent oppløsning i m-kresol ved 25° C. Når polyaminotriazoler fremstilles ved re-aksjonen mellom dihydrazidet og vandig hydrazin, innbefatter de foretrukne betin-gelser for å oppnå et produkt av en molekylvekt som svarer til en spesifikk viskositet som angitt foran, en temperatur mellom omtrent 140 og 260° C, en mengde hydrazin mellom omtrent 30 og 33 vektsprosent og en mengde vann mellom omtrent 6 og 7 pst., begge basert på vekten av dihydrazidet, samt en reaksjonsperiode på mellom Polyaminotriazoles for use in accordance with this invention preferably have a specific viscosity of at least 0.3, for example from 0.3 to 0.7, in a 0.1% by weight solution in m-cresol at 25° C. When polyaminotriazoles are prepared in the reaction between the dihydrazide and aqueous hydrazine, the preferred conditions for obtaining a product of a molecular weight corresponding to a specific viscosity as indicated above include a temperature between about 140 and 260°C, an amount of hydrazine between about 30 and 33 percent by weight and an amount of water between about 6 and 7 percent, both based on the weight of the dihydrazide, and a reaction period of between
18 og 24 timer. 18 and 24 hours.
Polyaminotriazoler egnet for anvendelse i samsvar med denne oppfinnelse, kan fremstilles på andre måter, for eksempel ved reaksjon mellom et mol av en dikarboksylsyre og mere enn to mol vandig hydrazin. Polyaminotriazoles suitable for use in accordance with this invention can be prepared in other ways, for example by reaction between one mole of a dicarboxylic acid and more than two moles of aqueous hydrazine.
En fullstendig beskrivelse av de polyaminotriazoler som er egnet for anvendelse i samsvar med denne oppfinnelse, samt fremgangsmåtene for fremstilling av slike polyaminotriazoler kan finnes i de ame-rikanske patenter nr. 2 512 601 og 2 512 667. A complete description of the polyaminotriazoles which are suitable for use in accordance with this invention, as well as the methods for producing such polyaminotriazoles can be found in the American patents no. 2,512,601 and 2,512,667.
Aminosubstituerte triaziner danner en annen egnet klasse av amidinforbindelser. Amino-substituted triazines form another suitable class of amidine compounds.
De foretrukne forbindelser i denne klasse er aminosubstituerte derivater av symmetriske triaziner, deri innbefattet gu-anaminer (2,4-diamino-sym.triaziner), melamin (2,4,6-triamino-sym.triazin) og substituerte melaminer. Aminogruppene kan være primære, sekundære eller terti-ære, og andre substituenter såsom hydrok-sylsubstituenter kan være tilstede. Blant spesielle forbindelser som er egnet, er 2,4-diamino-6-fenyl-sym.-triazin (benzoguanamin), 2,4-diamino-6-metyl-sym.-triazin, 2,4-diamino-6-butyl-sym.-triazin, 2,4-di-amino-6-benzyloksy-sym.-triazin, 2,4-di-amino-6-butoksy-sym.-triazin, 2,4-diami-no-6-cycloheksyloksy-sym.-triazin, 2,4-di-amino-6-klor-sym.-triazin, 2,4-diamino-6-mercapto-sym.-triazin, 2,4-dihydroksy-6-åmino-sym.-triazin (ammelid), 2-hydrok-sy-4,6-diamino-sym.-triazin (ammelin), N,N,N',N'-tetracyanoetyl-benzoguanamin, 2,4,6-triamino-sym.-triazin (melamin), fe-nylmelamin, butylmelamin, N,N-difenyl-melamin,- N.N-diallylmelamin, N,N',N"-tri-fenylmelamin og N,N',N"-trimetylmelamin. The preferred compounds in this class are amino-substituted derivatives of symmetrical triazines, including gu-anamines (2,4-diamino-sym.triazines), melamine (2,4,6-triamino-sym.triazine) and substituted melamines. The amino groups may be primary, secondary or tertiary, and other substituents such as hydroxyl substituents may be present. Among particular compounds suitable are 2,4-diamino-6-phenyl-sym.-triazine (benzoguanamine), 2,4-diamino-6-methyl-sym.-triazine, 2,4-diamino-6-butyl -sym.-triazine, 2,4-di-amino-6-benzyloxy-sym.-triazine, 2,4-di-amino-6-butoxy-sym.-triazine, 2,4-diami-no-6- cyclohexyloxy-sym.-triazine, 2,4-di-amino-6-chloro-sym.-triazine, 2,4-diamino-6-mercapto-sym.-triazine, 2,4-dihydroxy-6-amino-sym. .-triazine (ammelide), 2-hydroxy-sy-4,6-diamino-sym.-triazine (ammelin), N,N,N',N'-tetracyanoethyl-benzoguanamine, 2,4,6-triamino-sym. .-triazine (melamine), phenylmelamine, butylmelamine, N,N-diphenylmelamine, N,N-diallylmelamine, N,N',N"-tri-phenylmelamine and N,N',N"-trimethylmelamine.
Forbindelser med en imidazolinkjerne danner ytterligere en annen egnet klasse av amidinforbindelser. Egnete forbindelser av denne klasse innbefatter slike med formelen Compounds with an imidazoline nucleus form yet another suitable class of amidine compounds. Suitable compounds of this class include those of the formula
hvor R, og R2 er monofunksjonelle radika-ler. En særlig egnet klasse forbindelser er slike hvori R, er en langkjedet alifatisk hydrokarbongruppe såsom en alkylgruppe, en monoolefingruppe eller en diolefingrup-pe. R2 kan være et kortkjedet alifatisk radikal og kan inneholde andre funksjonelle grupper, såsom omega-hydroksygrupper eller omega-amingrupper. 2-aminoetylgrup-per og 2-hydroksyetylgrupper foretrekkes ved R2-posisjonen. where R, and R2 are monofunctional radicals. A particularly suitable class of compounds are those in which R 1 is a long-chain aliphatic hydrocarbon group such as an alkyl group, a monoolefin group or a diolefin group. R 2 may be a short-chain aliphatic radical and may contain other functional groups, such as omega-hydroxy groups or omega-amine groups. 2-aminoethyl groups and 2-hydroxyethyl groups are preferred at the R2 position.
Blant spesielle imidazolinforbindelser av den forannevnte formel som er egnet, er slike som finnes i handelen under «Nal-camines», deri innbefattet «Nalcamine G-11», hvori R2 er en 2-hydroksyetylgruppe og R, er en blanding av 11, 13, 15 og 17 kullstoffalifatiske grupper, «Nalcamine G-12» hvori R2 er en 2-hydroksyetylgruppe og R, en blanding av heptadecenyl- og hepta-decadienyl-radikal, «Nalcamine G-13» hvor R2 er en 2-hydroksyetylgruppe og er en heptadecenylgruppe, «Nalcamine G-14» hvor R2 er en 2-hydroksyetylgruppe og R, er en blanding av pentadecylgruppe og heptadecylgruppe, og «Nalcamine G-39M» hvor R2 er en 2-aminoetylgruppe og R, er en blanding av heptadecenylgruppe og hep-tadecadienylgruppe. Andre egnete imidazolinforbindelser innbefatter forbindelser av den forannevnte formel, hvor R, er hydrogen eller en lavere alkylgruppe, såsom metylgruppe, etylgruppe, isopropyl-gruppe, eller butylengruppe. Among particular imidazoline compounds of the above formula which are suitable are those found commercially under "Nal-camines", including "Nalcamine G-11", in which R 2 is a 2-hydroxyethyl group and R is a mixture of 11, 13 , 15 and 17 carbon aliphatic groups, "Nalcamine G-12" where R2 is a 2-hydroxyethyl group and R, a mixture of heptadecenyl and hepta-decadienyl radicals, "Nalcamine G-13" where R2 is a 2-hydroxyethyl group and is a heptadecenyl group, "Nalcamine G-14" where R2 is a 2-hydroxyethyl group and R is a mixture of pentadecyl group and heptadecyl group, and "Nalcamine G-39M" where R2 is a 2-aminoethyl group and R is a mixture of heptadecenyl group and heptadecadienyl group. Other suitable imidazoline compounds include compounds of the above formula, where R 1 is hydrogen or a lower alkyl group, such as methyl group, ethyl group, isopropyl group, or butylene group.
I samsvar med en foretrukket utfø-relse for denne oppfinnelse innblandes den forannevnte amidinforbindelse i en oksymetylenpolymer som inneholder både ok-symetylengrupper og oksyalkylengrupper med tilstøtende kullstoffatomer, idet ok-symetylenpolymerén fortrinsvis inneholder fra 60 til 99,6 molprosent av gjentatte ok-symetylengrupper. Det fremgår at oksy-metylenpolymerenes ømfindtlighet overfor termisk stabilisering ved tilsetning av de forannevnte amidinforbindelser er særlig høy, når oksymetylenpolymeren inneholder oksyalkylenenheter med tilstøtende kullstoffatomer og er oppnådd fra sykliske etere med direkte bundne kullstoffatomer. In accordance with a preferred embodiment of this invention, the aforementioned amidine compound is mixed into an oxymethylene polymer containing both oxy-symethylene groups and oxyalkylene groups with adjacent carbon atoms, the oxy-symethylene polymer preferably containing from 60 to 99.6 mole percent of repeated oxy-symethylene groups. It appears that the sensitivity of the oxymethylene polymers to thermal stabilization by addition of the aforementioned amidine compounds is particularly high when the oxymethylene polymer contains oxyalkylene units with adjacent carbon atoms and is obtained from cyclic ethers with directly bonded carbon atoms.
Blant de oksymetylenpolymerer sor%. anvendes i samsvar med denne utførelse;' for oppfinnelsen er slike som har en struktur som omfatter gjentatte enheter av formelen Among the oxymethylene polymers sor%. used in accordance with this embodiment;' for the invention are those which have a structure comprising repeated units of the formula
hvor n er et helt tall fra 0 til 5 og hvor n er 0 fra 60 til 99,6 pst. av de gjentatte enheter. Foretrukne oksymetylenpolymerer er, slike som har en struktur som omfatter gjentatte enheter av oksymetylen og ok-syetylen, hvori fra 60 til 99,6 pst. av de gjentatte enheter er oksymetylenenheter. Slike oksymetylenpolymerer fremstilles ved å sampolymerisere trioksan med en syklisk eter av strukturen CH2 O where n is an integer from 0 to 5 and where n is 0 from 60 to 99.6 percent of the repeated units. Preferred oxymethylene polymers are those which have a structure comprising repeating units of oxymethylene and oxyethylene, in which from 60 to 99.6 per cent of the repeating units are oxymethylene units. Such oxymethylene polymers are produced by copolymerizing trioxane with a cyclic ether of the structure CH2 O
CH2 (OCH2)n hvor n er et helt tall fra null til to. Blandt de spesielle sykliske etere som kan anvendes, er etylenoksyd, 1,3-dioksolan, 1,3,5-trioksepan, 1,3-dioksan, trimetylenoksyd, pentametylenoksyd, 1,2-propylenoksyd, 1,2-butylenoksyd, neopentylformal, pentaery-tritoldiformal, paraldehyd, tetrahydrofu-ran og butadienmonoksyd. CH2 (OCH2)n where n is an integer from zero to two. Among the particular cyclic ethers that can be used are ethylene oxide, 1,3-dioxolane, 1,3,5-trioxepane, 1,3-dioxane, trimethylene oxide, pentamethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, neopentyl formal, pentaerythritol diformal, paraldehyde, tetrahydrofuran and butadiene monoxide.
De foretrukne katalysatorer som anvendes under fremstilling av de ønskete sampolymerer er borfluoridkoordinatkom-pleksene med organiske forbindelser hvori oksygen eller svovel er donoratomet. Koordinatkomplekset av borfluorid kan for eksempel være et kompleks med en fenol, en eter, en ester eller et dialkylsulfid. Borfluorid-dibutyleterat, koordinatkomplekset av borfluorid med dibutyleter, er det foretrukne koordinatkompleks. Borfluoridkom-l lekset med dietyleter er likeledes meget effektivt. Andre borfluoridkomplekser som kan anvendes, er kompleksene med metyl-acetat, med etylacetat, med fenylacetat, med dimetyleter, med metylfenyleter og med dimetylsulfid. Koordinatkomplekset av borfluorid bør være tilstede i polymerisasjonssonen i slike mengder at dens bor-fluoridinnhold er mellom 0,001 og 1,0 vektsprosent, basert på vekten av monomerene i polymerisasjonssonen. Fortrinsvis bør det anvendes mengder mellom omtrent 0,003 og omtrent 0,1 vektsprosent. The preferred catalysts used in the production of the desired copolymers are the boron fluoride coordination complexes with organic compounds in which oxygen or sulfur is the donor atom. The coordinate complex of boron fluoride can, for example, be a complex with a phenol, an ether, an ester or a dialkyl sulphide. Boron fluoride dibutyl etherate, the coordination complex of boron fluoride with dibutyl ether, is the preferred coordination complex. Boron fluoride combined with diethyl ether is also very effective. Other boron fluoride complexes that can be used are the complexes with methyl acetate, with ethyl acetate, with phenyl acetate, with dimethyl ether, with methyl phenyl ether and with dimethyl sulphide. The boron fluoride coordinate complex should be present in the polymerization zone in such amounts that its boron fluoride content is between 0.001 and 1.0 percent by weight, based on the weight of the monomers in the polymerization zone. Preferably, amounts between about 0.003 and about 0.1 percent by weight should be used.
Monomerene i reaksjonssonen er fortrinsvis vannfri eller stort sett vannfri. Mindre mengder fuktighet, slik som kan være tilstede i handelsrene reagenser eller kan innføres ved kontakt med atmosfære-luft, vil ikke hindre polymerisering, men bør fjernes for å oppnå oksymetylenpolymerer av den høyeste molekylvekt. The monomers in the reaction zone are preferably anhydrous or largely anhydrous. Minor amounts of moisture, such as may be present in commercially pure reagents or may be introduced by contact with atmospheric air, will not prevent polymerization, but should be removed to obtain oxymethylene polymers of the highest molecular weight.
Trioksanet, den sykliske eter og kata- The trioxane, the cyclic ether and cata-
lysatoren kan oppløses i et felles vannfritt oppløsningsmiddel, såsom cykloheksan, og bringes til å reagere i en lukket reaksjons-sone. Temperaturen i reaksjonssonen kan variere fra omtrent 0° C til omtrent 100° C. Lengden av reaksjonstid kan variere fra omtrent 5 minutter til omtrent 72 timer. Trykk fra vakuum til omtrent 100 atmos-færer eller høyere kan anvendes, selv om atmosfæretrykk foretrekkes. the lysator can be dissolved in a common anhydrous solvent, such as cyclohexane, and reacted in a closed reaction zone. The temperature in the reaction zone can vary from about 0° C. to about 100° C. The length of reaction time can vary from about 5 minutes to about 72 hours. Pressures from vacuum to about 100 atmospheres or higher can be used, although atmospheric pressure is preferred.
Man har funnet at de forholdsvis små mengder av annen syklisk eter enn trioksan som anvendes i sampolymeriseringsreak-sjonen, som regel forsvinner fullstendig fra reaksjonsblandingen. Det ønskete forhold mellom trioksan og syklisk eter i reaksjonsblandingen kan derfor bestemmes grovt for et ønsket molforhold i oksymetylenpolymeren ved å anta at all syklisk eter oppbrukes og ved å gå ut fra et bestemt omdannelsesnivå ut fra tidligere erfarin-ger under tilnærmet sammenliknbare be-tingelser. It has been found that the relatively small amounts of cyclic ether other than trioxane used in the copolymerization reaction usually disappear completely from the reaction mixture. The desired ratio between trioxane and cyclic ether in the reaction mixture can therefore be roughly determined for a desired molar ratio in the oxymethylene polymer by assuming that all cyclic ether is used up and by starting from a specific conversion level based on previous experiences under roughly comparable conditions.
Den sykliske eters kjemiske konstitu-sjon må også tas i betraktning. Således inneholder 1,3-dioksolan både en oksymety-lengruppe og en oksyetylengruppe. Dets opptakelse i sampolymermolekylet gir både oksymetylenenheten og oksyetylenenheten i polyoksymetylenmolekylet. The chemical constitution of the cyclic ether must also be taken into account. Thus, 1,3-dioxolane contains both an oxymethylene group and an oxyethylene group. Its inclusion in the copolymer molecule provides both the oxymethylene unit and the oxyethylene unit in the polyoxymethylene molecule.
Rent generelt er den sykliske eter tilstede i reaksjonsblandingen i mengder mellom 0,2 og 30 molprosent, basert på total-antallet mol av monomer. Den optimale andel vil avhenge av den spesielle oksymetylenpolymer som ønskes, den forventete omdannelsesgrad og den kjemiske konsti-tusjon for den anvendte sykliske eter. Generally speaking, the cyclic ether is present in the reaction mixture in amounts between 0.2 and 30 mole percent, based on the total number of moles of monomer. The optimum proportion will depend on the particular oxymethylene polymer desired, the expected degree of conversion and the chemical constitution of the cyclic ether used.
Ved fullføring av polymeriseringsreak-sjonen er det ønskelig å nøytralisere akti-viteten for polymeriseringskatalysatoren, fordi lengre tids kontakt med katalysato-ren spalter polymeren. Polymerisasjons-produktet kan behandles med en alifatisk amin, såsom tri-n-butylamin, i et støkio-metrisk overskudd ut over mengden av fri katalysator i reaksjonsproduktet, og fortrinsvis i en organisk vaskevæske som danner et oppløsningsmiddel for ureagert trioksan. Eller hvis dette ønskes, kan reaksjonsproduktet vaskes med vann som nøy-traliserer katalysatoraktiviteten. Upon completion of the polymerization reaction, it is desirable to neutralize the activity of the polymerization catalyst, because prolonged contact with the catalyst splits the polymer. The polymerization product can be treated with an aliphatic amine, such as tri-n-butylamine, in a stoichiometric excess over the amount of free catalyst in the reaction product, and preferably in an organic washing liquid which forms a solvent for unreacted trioxane. Or, if desired, the reaction product can be washed with water, which neutralizes the catalyst activity.
I tillegg til amidinforbindelsen kan det i oksymetylenpolymeren inkorporeres andre stoffer med den virkning å forbedre In addition to the amidine compound, other substances with the effect of improving can be incorporated into the oxymethylene polymer
oksymetylenpolymerens termiske stabilitet. the thermal stability of the oxymethylene polymer.
Vinylpolymerer med sidekjeder som inneholder strukturen -CO-N=, slik som i amidgrupper og lactamgrupper, er egnet i denne forbindelse. Spesielt egnete polymerer av denne type er homopolymerer og sampolymerer av vinylpyrolidon, vinyl-2-metylpyrolidon, akrylamid og substituerte akrylamider, N-vinyl-kaprolactam, N-vinyl-piperidon, N-vinylacetanilid, N-vinyl-n-metylacetamid, Vinyl polymers with side chains containing the structure -CO-N=, such as in amide groups and lactam groups, are suitable in this connection. Particularly suitable polymers of this type are homopolymers and copolymers of vinylpyrrolidone, vinyl-2-methylpyrrolidone, acrylamide and substituted acrylamides, N-vinyl-caprolactam, N-vinyl-piperidone, N-vinylacetanilide, N-vinyl-n-methylacetamide,
N-allylamider og N-metallylamider og N-vinyl-N-fenylacetamid, idet polymerene fortrinsvis har molekylvekter mellom 20 000 og 500 000. I sampolymerene kan sampolymeren også inneholde strukturen -CO-N=. Egnete sampolymerer for anvendelse sammen med for eksempel vinylpyr-rolidon er vinylacetat, styren, metylakrylat, etylakrylat og butylakrylat, metylmetakry-lat, vinylcarbazol, natriumakrylat, meta-krylonitril og akrylonitril. Mengden av anvendt vinylpolymer overskrider ikke 10 pst. og kan som regel ligge mellom 0,1 og 2 pst. basert på vekten av oksymetylenpolymeren. N-allylamides and N-methylylamides and N-vinyl-N-phenylacetamide, the polymers preferably having molecular weights between 20,000 and 500,000. In the copolymers, the copolymer can also contain the structure -CO-N=. Suitable copolymers for use together with, for example, vinyl pyrrolidone are vinyl acetate, styrene, methyl acrylate, ethyl acrylate and butyl acrylate, methyl methacrylate, vinyl carbazole, sodium acrylate, methacrylonitrile and acrylonitrile. The amount of vinyl polymer used does not exceed 10% and can usually be between 0.1 and 2% based on the weight of the oxymethylene polymer.
Proteiner kan også anvendes for å øke den termiske stabilitet for oksymetylen-polymerene, særlig dem som inneholder både -CH20-enheter og oksyalkylenenheter med tilstøtende kullstoffatomer. Egnete proteiner er gelatin, lim, kasein, albuminer, globuliner, gluteliner og keratiner. Protei-nene kan være i deres naturlige tilstand eller kan være kjemisk modifisert for å øke deres oppløselighet, for eksempel ved par-tiell hydrolyse. Mengden av anvendt pro-tein overskrider ikke 10 pst. og kan som regel ligge mellom 0,1 og 2 pst., basert på vekten av oksymetylenpolymeren. Proteins can also be used to increase the thermal stability of the oxymethylene polymers, particularly those containing both -CH 2 O units and oxyalkylene units with adjacent carbon atoms. Suitable proteins are gelatin, glue, casein, albumins, globulins, glutelins and keratins. The proteins may be in their natural state or may be chemically modified to increase their solubility, for example by partial hydrolysis. The amount of protein used does not exceed 10 percent and can usually lie between 0.1 and 2 percent, based on the weight of the oxymethylene polymer.
I en foretrukket utførelse for oppfinnelsen kan polymerblandingen foruten en amidinforbindelse inneholde en fenolfor-bindelse og fortrinsvis en alkylenbisfenol, som er kjent å virke som termiske stabilisatorer i oksymetylenpolymerer. Det fremgår at stabiliseringsvirkningen for amidinforbindelsene og for fenolforbindelsene virker fremmende på hverandre, så at en blanding av en stabilisator fra hver klasse er mere effektiv enn en sammenliknbar mengde stabilisator fra hver klasse i og for seg. På samme måte øker fenolforbindelsene stabiliseringsvirkningen for vinylpo-lymerene og proteiner slik som nevnt foran. In a preferred embodiment for the invention, in addition to an amidine compound, the polymer mixture may contain a phenol compound and preferably an alkylene bisphenol, which is known to act as thermal stabilizers in oxymethylene polymers. It appears that the stabilizing effect of the amidine compounds and of the phenol compounds promote each other, so that a mixture of a stabilizer from each class is more effective than a comparable amount of stabilizer from each class in and of itself. In the same way, the phenolic compounds increase the stabilization effect for the vinyl polymers and proteins as mentioned above.
En egnet klasse alkylenbisfenoler innbefatter forbindelser med fra 1 til 4 kullstoffatomer i alkylengruppen og med fra 0 til 2 alkylsubstituenter på hver benzen-ring, idet hver alkylsubstituent har fra 1 til 4 kullstoffatomer. De foretrukne alkylenbisfenoler er 2,2'-metylen-bis-(4-metyl-6-tertiærbutylfenol) og 4,4'-butyliden-bis-(6-tertiærbutyl-3-metylfenol). Egnete fenoliske stabilisatorer andre enn alkylenbisfenoler innbefatter 2,6-ditertiærbutyl-4-metylfenol, oktylfenyl og p-fenylfenol. A suitable class of alkylene bisphenols includes compounds with from 1 to 4 carbon atoms in the alkylene group and with from 0 to 2 alkyl substituents on each benzene ring, each alkyl substituent having from 1 to 4 carbon atoms. The preferred alkylene bisphenols are 2,2'-methylene-bis-(4-methyl-6-tertiary-butylphenol) and 4,4'-butylidene-bis-(6-tertiary-butyl-3-methylphenol). Suitable phenolic stabilizers other than alkylene bisphenols include 2,6-di-tertiarybutyl-4-methylphenol, octylphenyl and p-phenylphenol.
Amidinforbindelsen blandes som regel sammen med oksymetylenpolymeren i mengder som ikke overskrider 5 pst. basert på vekten av oksymetylenpolymer, og fortrinsvis i mengder mellom omtrent 0,01 og 1 vektsprosent. Alkylenbisfenolen, når denne brukes, innblandes i mengder som ikke overskrider 5 vektsprosent og fortrinsvis fra omtrent 1 til omtrent 0,1 vektsprosent. The amidine compound is usually mixed with the oxymethylene polymer in amounts not to exceed 5 percent based on the weight of the oxymethylene polymer, and preferably in amounts between about 0.01 and 1 percent by weight. The alkylene bisphenol, when used, is incorporated in amounts not exceeding 5 percent by weight and preferably from about 1 to about 0.1 percent by weight.
Amidinforbindelsene og alkylenbisfenolen, kan om ønskes blandes intimt med oksymetylenpolymeren ved å tilføres i opp-løsning i et egnet oppløsningsmiddel til det findelte faste oksymetylenpolymer et-terfulgt av fordampning av oppløsnings-midlet. The amidine compounds and the alkylene bisphenol can, if desired, be intimately mixed with the oxymethylene polymer by being added in solution in a suitable solvent to the finely divided solid oxymethylene polymer followed by evaporation of the solvent.
Innblandingen kan også foretas ved tørrblanding av den findelte oksymetylenpolymer og de findelte stabilisatorer og ved å male stabilisatorene inn i oksymetylenpolymeren når den sistnevnte bearbei-des på en gummimølle. The mixing can also be done by dry mixing the finely divided oxymethylene polymer and the finely divided stabilizers and by grinding the stabilizers into the oxymethylene polymer when the latter is processed on a rubber mill.
En meget egnet og effektiv måte til å inkorporere den termiske stabilisator består i å dispergere stabilisatoren på over-flatene av partikler av den faste oksymetylenpolymer og deretter å underkaste oksymetylenpolymeren varme og trykk mens den presses gjennom en innsnevret dyse i en formeoperasjon, for eksempel under fremstilling av en ekstrudert stang. Blandingene ifølge denne oppfinnelse kan om ønskes inneholde mykningsmidler, fyllstoffer, pigmenter og andre stabilisatorer, såsom benzofenolderivater som er stabilisatorer overfor spaltning av ultrafiolett lys. Oksymetylenpolymeren kan stabi-liseres mot spaltning ved ultrafiolett lys ved tilsetning av for eksempel omtrent 1 vektsprosent 2,2'-dihydroksy-4,4'-dimetok-sy-benzofenon. A very suitable and effective way to incorporate the thermal stabilizer consists of dispersing the stabilizer on the surfaces of particles of the solid oxymethylene polymer and then subjecting the oxymethylene polymer to heat and pressure while being forced through a constricted die in a molding operation, for example during manufacture of an extruded rod. The mixtures according to this invention can, if desired, contain softeners, fillers, pigments and other stabilizers, such as benzophenol derivatives which are stabilizers against decomposition by ultraviolet light. The oxymethylene polymer can be stabilized against decomposition by ultraviolet light by adding, for example, approximately 1% by weight of 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone.
De etterfølgende eksempler illustrerer oppfinnelsen: The following examples illustrate the invention:
Eksempel 1. Example 1.
Trioksan ble polymerisert chargevis i et sigmabladet knadeapparat i blanding med en fjerdedel av dets vekt av cykloheksan og 0,0175 ganger dets vekt av di-oksalan. 65 deler pr. million borfluorid-di-butyleterat som katalysator var tilstede i blandingen. Reaksjonsblandingen ble holdt ved en temperatur mellom 54 og 55° C i ytterligere 100 minutter. Den dannete oksymetylenpolymer hadde en spesifikk viskositet på 1,6 (målt ved 60° C i 0,1 vektsprosent oppløsning i p-klorfenol som inneholdt 2 vektsprosent alfapinen). Trioxane was polymerized batchwise in a sigma blade kneader in admixture with a quarter of its weight of cyclohexane and 0.0175 times its weight of dioxalane. 65 parts per million boron fluoride dibutyl etherate as a catalyst was present in the mixture. The reaction mixture was maintained at a temperature between 54 and 55°C for a further 100 minutes. The oxymethylene polymer formed had a specific viscosity of 1.6 (measured at 60°C in a 0.1% by weight solution in p-chlorophenol containing 2% by weight of alphapinene).
Femti vektsdeler av den foran beskrevne oksymetylenpolymer, 0,25 deler cyanoguanidin og 0,25 deler 2,2'-metylen-bis(4-metyl-6-tertiærbutylfenol) ble malt ved 200 til 202° C i 45 minutter i et oppvarmet kammer utstyrt med et blandeapparat av sigmabladtypen. Fifty parts by weight of the oxymethylene polymer described above, 0.25 parts cyanoguanidine and 0.25 parts 2,2'-methylene-bis(4-methyl-6-tertiary-butylphenol) were ground at 200 to 202°C for 45 minutes in a heated chamber equipped with a sigma blade type mixer.
Den termiske spaltningshastighet for den således behandlete oksymetylenpolymer (når det ble holdt i et åpent kar i en ovn med sirkulerende luft ved 222° C og målt uten uttak av prøven fra ovnen) var 0,00 vektsprosent i minuttet i de første 18 minutter og 0,04 vektsprosent pr. mi-nutt for resten. Forut for behandlingen hadde sampolymeren en spaltningshastighet på 4 vektsprosent i minuttet. The thermal decomposition rate of the oxymethylene polymer thus treated (when held in an open vessel in a circulating air oven at 222°C and measured without removing the sample from the oven) was 0.00 weight percent per minute for the first 18 minutes and 0 .04 weight percent per mi-nutt for the rest. Prior to treatment, the copolymer had a decomposition rate of 4% by weight per minute.
Eksempel 2. Example 2.
Eksempel 1 ble gjentatt bortsett fra at mengden av cyanoguanidin ble redusert til 0,05 deler. Den termiske spaltningshastighet (målt som foran) var 0,00 vektsprosent i minuttet i de første 18 minutter og 0,04 vektsprosent i minuttet for resten. Example 1 was repeated except that the amount of cyanoguanidine was reduced to 0.05 parts. The thermal decomposition rate (measured as before) was 0.00 wt% per minute for the first 18 minutes and 0.04 wt% per minute for the remainder.
Eksempel 3. Example 3.
Eksempel 1 ble gjentatt, bortsett fra at begge stabilisatorer ble redusert til en mengde på 0,10 deler. Den termiske spaltningshastighet var 0,01 vektsprosent i minuttet for hele prøven. Example 1 was repeated, except that both stabilizers were reduced to an amount of 0.10 parts. The thermal decomposition rate was 0.01% by weight per minute for the entire sample.
Eksempel 4. Example 4.
Cyanoguanidin (0,1 vektsprosent) og 2,2'-metylen-bis- (4-metyl-6-tertiærbutyl-fenol) (0,5 vektsprosent) ble innblandet i en polypksymetylen-homopolymer i et oppvarmet kammer med motsatt roterende dobbeltskruer for knadning. Spaltningshastigheten (målt slik som foran) var 0,9 vektsprosent i minuttet. Cyanoguanidine (0.1% by weight) and 2,2'-methylene-bis-(4-methyl-6-tertiarybutyl-phenol) (0.5% by weight) were mixed into a polyoxymethylene homopolymer in a heated chamber with counter-rotating twin screws for gnawing. The decomposition rate (measured as before) was 0.9% by weight per minute.
Eksempel 5. Example 5.
Trioksan ble polymerisert ved 60° C i 75 minutter i et knadeapparat med sigma-blader i blanding med 3/7 av dets vekt av cykloheksan, 2,5 pst. av dets vekt av dioksolan og 0,021 pst. av dets vekt av borfluo-riddibutyl-etenat. Reaksjonsproduktet ble vasket med aceton som inneholdt en mindre mengde dibutylamin. Den tørkete oksymetylenpolymer andro til 57,8 pst. ut-bytte basert på totale monomerer og inneholdt 4,2 vektsprosent monomerenheter oppnådd fra dioksolan. Trioxane was polymerized at 60°C for 75 minutes in a sigma blade kneader in a mixture with 3/7 of its weight of cyclohexane, 2.5% of its weight of dioxolane and 0.021% of its weight of boron fluoride dibutyl -ethenate. The reaction product was washed with acetone containing a small amount of dibutylamine. The dried oxymethylene polymer yielded 57.8% yield based on total monomers and contained 4.2% by weight monomer units derived from dioxolane.
En polyaminotriazol av isosebacinsyre med en indre viskositet på omtrent 0,4 i m-kresol (0,1 vektsprosent oppløsning ved 25° C) ble fremstillet ved reaksjon mellom 100 g isosebacinsyre og 70 ml hydrazinhy-drat i en autoklav. Autoklaven ble oppvarmet til 220° C i 18 timer og 260° C i 3 timer. Trykket nådde 70 kg/cm2 under reaksjo-nen. A polyaminotriazole of isosebacic acid with an intrinsic viscosity of about 0.4 in m-cresol (0.1% by weight solution at 25°C) was prepared by reaction between 100 g of isosebacic acid and 70 ml of hydrazine hydrate in an autoclave. The autoclave was heated to 220° C. for 18 hours and 260° C. for 3 hours. The pressure reached 70 kg/cm2 during the reaction.
Tre vektsdeler av den foran beskrevne trioksandioksolan-oksymetylenpolymer ble oppslemmet med en oppløsning av 0,06 deler av den foran beskrevne polyaminotriazol i omtrent 12 deler metanol. Man lot me-tanolen fordampe ved værelsestemperatur under gjentatt omrøring, hvoretter polymeren ble tørket ved 65° C i 2 timer. Fra dette materiale ble det trykkstøpt en skive i 4'minutter ved 190° C og 105 kg/cm2. Ski-ven hadde en termisk spaltningshastighet (når den ble holdt i et åpent kar i en ovn med sirkulerende luft ved 222° C) på 0,63 vektsprosent i minuttet for de første 18 pst. av polymeren og 0,47 vektsprosent i minuttet for resten. Den termiske spaltningshastighet for oksymetylenpolymeren innen behandling med polyaminotriazolen var 1,3 vektsprosent i minuttet. Three parts by weight of the trioxanedioxolane-oxymethylene polymer described above were slurried with a solution of 0.06 parts of the polyaminotriazole described above in about 12 parts methanol. The methanol was allowed to evaporate at room temperature with repeated stirring, after which the polymer was dried at 65° C. for 2 hours. From this material, a disc was pressure molded for 4 minutes at 190° C and 105 kg/cm2. The disc had a thermal decomposition rate (when held in an open vessel in a circulating air oven at 222°C) of 0.63 weight percent per minute for the first 18 percent of the polymer and 0.47 weight percent per minute for the rest. The thermal decomposition rate of the oxymethylene polymer within treatment with the polyaminotriazole was 1.3 weight percent per minute.
Eksempel 6. Example 6.
Polyaminotriazolen ifølge eksempel 5 og en tilsvarende polyaminotriazol fremstillet av sebacinsyre ble hver for seg in-korporert i en prøve av en sampolymer av trioksan og dioksolan (med 4,5 vektsprosent av monomerenheter oppnådd fra dioksolan) sammen med 2,2'-metylen-bis-(4-metyl-6-tertiærbutylfenol). Det ble anvendt 0,5 vektsprosent av hver stabilisator og innblandet i oksymetylenpolymeren ved oppmaling i luft i 45 minutter ved 200° C. Prøven som inneholdt polyaminotriazolen fra sebacinsyre hadde en termisk spaltningshastighet på 0,08 vektsprosent i minuttet, mens prøven som inneholdt polyaminotriazolen fra isosebacinsyre hadde en termisk spaltningshastighet på 0,04 vektsprosent i minuttet (begge målt som beskrevet foran). The polyaminotriazole according to Example 5 and a corresponding polyaminotriazole prepared from sebacic acid were separately incorporated into a sample of a copolymer of trioxane and dioxolane (with 4.5% by weight of monomer units obtained from dioxolane) together with 2,2'-methylene-bis -(4-methyl-6-tertiarybutylphenol). 0.5% by weight of each stabilizer was used and mixed into the oxymethylene polymer by grinding in air for 45 minutes at 200° C. The sample containing the polyaminotriazole from sebacic acid had a thermal decomposition rate of 0.08% by weight per minute, while the sample containing the polyaminotriazole from isosebacic acid had a thermal decomposition rate of 0.04% by weight per minute (both measured as described above).
Eksempel 7. Example 7.
Firti vektsdeler av en trioksan-dioksolan-sampolymer med 5 vektsprosent av monomerenheter oppnådd fra dioksolan og med en spesifikk viskositet på 1,8, 0,4 deler benzoguanamin og 0,4 deler 2,2'-metylen-bis- (4-metyl-6-tertiærbutylfenol) ble oppmalt i et oppvarmet kammer utstyrt med et blandeapparat av sigmabladtypen i 45 minutter ved 200 til 202° C. Den således behandlete oksymetylenpolymer hadde en spaltningshastighet (regnet etter vektstap i minuttet når det ble holdt i et åpent kar i en ovn med sirkulerende luft ved 222° C) på 0,05 vektsprosent i minuttet. Spaltningshastigheten innen behandling var 3,2 vektsprosent i minuttet. Forty parts by weight of a trioxane-dioxolane copolymer with 5% by weight of monomer units obtained from dioxolane and having a specific viscosity of 1.8, 0.4 parts of benzoguanamine and 0.4 parts of 2,2'-methylene-bis-(4-methyl -6-tertiarybutylphenol) was milled in a heated chamber equipped with a sigma blade type mixer for 45 minutes at 200 to 202° C. The oxymethylene polymer thus treated had a decomposition rate (calculated by weight loss per minute when held in an open vessel in a oven with circulating air at 222° C) of 0.05 percent by weight per minute. The rate of decomposition within treatment was 3.2% by weight per minute.
Eksempel 8. Example 8.
■Eksempel 7 ble gjentatt, bortsett fra at den fenoliske stabilisator var 4,4'-butyl-iden-bis-(6-tertiærbutyl-3-metylfenol). Spaltningshastigheten for den behandlete oksymetylenpolymer var 0,04 vektsprosent i minuttet. Example 7 was repeated, except that the phenolic stabilizer was 4,4'-butyl-idene-bis-(6-tert-butyl-3-methylphenol). The decomposition rate of the treated oxymethylene polymer was 0.04 weight percent per minute.
Eksempel 9. Example 9.
Firti vektsdeler av en trioksan-dioksolan-sampolymer med 5,1 vektsprosent av monomerenheter oppnådd fra dioksolan og med en spesifikk viskositet på 1,4, 0,4 deler N,N-diallylmelamin og 0,4 deler 2,2'-metylen-bis- (4-metyl-6-tertiærbutylfenol) ble blandet ved omrøring og deretter oppmalt i 30 minutter ved 200 til 202° C under nitrogen i et oppvarmet kammer inneholdende et par motsatt roterende skruer. Skruene var tilnærmet av sylindrisk form og hadde begge en grunn skrueformet konkavitet med lang stigning. Kammeret ble oppvarmet ved å sirkulere varm olje gjennom dobbelte vegger. Ved fullføringen av denne behandling var den termiske spaltningshastighet for oksymetylenpolymeren (målt som foran) 0,00 vektsprosent i minuttet i de første 18 minutter og 0,02 vektsprosent i minuttet for resten. Forut for stabilise-ringen var spaltningshastigheten 3,0 vektsprosent i minuttet. Forty parts by weight of a trioxane-dioxolane copolymer with 5.1 weight percent of monomer units obtained from dioxolane and with a specific viscosity of 1.4, 0.4 parts of N,N-diallylmelamine and 0.4 parts of 2,2'-methylene- bis-(4-methyl-6-tertiarybutylphenol) was mixed with stirring and then milled for 30 minutes at 200 to 202°C under nitrogen in a heated chamber containing a pair of counter-rotating screws. The screws were approximately cylindrical in shape and both had a shallow helical concavity with a long pitch. The chamber was heated by circulating hot oil through double walls. At the completion of this treatment, the thermal decomposition rate of the oxymethylene polymer (measured as above) was 0.00 weight percent per minute for the first 18 minutes and 0.02 weight percent per minute for the remainder. Prior to stabilization, the cleavage rate was 3.0% by weight per minute.
Eksempel 10. Example 10.
Eksempel 9 ble gjentatt, bortsett fra at mengdene av stabilisatorer ble redusert til 0,04 deler N,N-diallylmelamin og 0,08 deler av den fenoliske stabilisator. Spaltningshastigheten etter behandling var 0,00 vektsprosent i minuttet i de første 18 minutter og 0,05 vektsprosent i minuttet for resten. Example 9 was repeated, except that the amounts of stabilizers were reduced to 0.04 parts of N,N-diallylmelamine and 0.08 parts of the phenolic stabilizer. The cleavage rate after treatment was 0.00 weight percent per minute for the first 18 minutes and 0.05 weight percent per minute for the remainder.
Eksempel 11. Example 11.
Fire hundre vektsdeler av oksymetylenpolymeren ifølge eksempel 9, 4 deler av N,N-diallylmelamin og 4 deler 2,2'-metylen-bis- (4-metyl-6-tertiærbutylfenol) ble blandet tørt til jevn blanding og deretter ekstrudert ved en trommeltemperatur på 182° C og en skruehastighet på 40 til 45 omdr/min. Ekstrudatet med en diameter på omtrent 3 mm ble oppkappet i stykker av en lengde på omtrent 6 mm. Stykkene ble plassert i et åpent kar i en ovn ved 160° C under en konstant strøm av nitrogen. Prøver av oksymetylenpolymeren ble ut-tatt med en times intervaller og undersøkt etter spaltningshastighet som beskrevet foran. Resultatene var som følger: Four hundred parts by weight of the oxymethylene polymer of Example 9, 4 parts of N,N-diallylmelamine and 4 parts of 2,2'-methylene-bis-(4-methyl-6-tertiary-butylphenol) were dry mixed to a uniform mixture and then extruded at a drum temperature at 182° C and a screw speed of 40 to 45 rpm. The extrudate with a diameter of about 3 mm was cut into pieces of about 6 mm in length. The pieces were placed in an open vessel in an oven at 160°C under a constant stream of nitrogen. Samples of the oxymethylene polymer were taken at one-hour intervals and examined for decomposition rate as described above. The results were as follows:
Eksempel 12. Example 12.
Eksempel 9 ble gjentatt, bortsett fra at melamin ble anvendt istedenfor N,N-diallylmelamin og oksymetylenpolymeren var en sampolymer av trioksan og dioksolan med 5,5 vektsprosent av enheter oppnådd fra det sistnevnte. Spaltningshastigheten for den behandlete oksymetylenpolymer ble funnet å være 0,02 vektsprosent i minuttet. Forut for behandlingen var spaltningshastigheten 2,2 vektsprosent i minuttet. Example 9 was repeated, except that melamine was used instead of N,N-diallylmelamine and the oxymethylene polymer was a copolymer of trioxane and dioxolane with 5.5% by weight of units derived from the latter. The decomposition rate of the treated oxymethylene polymer was found to be 0.02 weight percent per minute. Prior to treatment, the rate of decomposition was 2.2% by weight per minute.
Eksempel 13. Example 13.
Stearoguanamin (1,9 vektsprosent) og 2,2'-metylen-bis-(4-metyl-6-tertiærbutyl-fenol) (1 vektsprosent) ble innblandet i oksymetylenpolymeren ifølge eksempel 7 på den måte som er beskrevet deri. Den termiske spaltningshastighet for den således behandlete oksymetylenpolymer var 0,05 vektsprosent i minuttet. Stearoguanamine (1.9% by weight) and 2,2'-methylene-bis-(4-methyl-6-tertiarybutyl-phenol) (1% by weight) were mixed into the oxymethylene polymer of Example 7 in the manner described therein. The thermal decomposition rate of the oxymethylene polymer thus treated was 0.05 weight percent per minute.
Eksempel 14. Example 14.
Eksempel 9 ble gjentatt, bortsett fra at oksymetylenpolymeren heri ble erstattet av en trioksan-homopolymer med en rå termisk spaltningshastighet som lå over 10 vektsprosent i minuttet. — Spaltningshastigheten etter behandling var 0,57 vektsprosent i minuttet. Example 9 was repeated, except that the oxymethylene polymer herein was replaced by a trioxane homopolymer having a crude thermal decomposition rate in excess of 10 weight percent per minute. — The decomposition rate after treatment was 0.57 weight percent per minute.
Eksempel 15. Example 15.
Eksempel 9 ble gjentatt, bortsett fra at den fenoliske stabilisator ble utelatt. Spaltningshastigheten for den behandlete oksymetylenpolymer var 0,22 vektsprosent i minuttet. Example 9 was repeated, except that the phenolic stabilizer was omitted. The decomposition rate of the treated oxymethylene polymer was 0.22 weight percent per minute.
Eksempel 16. Example 16.
Femti deler av oksymetylenpolymeren ifølge eksempel 1 ble oppmalt ved 200 til 202° C i 45 minutter med 0,25 deler 2,2'-metylen-bis-(4-metyl-6-tertiærbutylfe-nol) og 0,05 deler «Nalcamine G-13» i et oppvarmet kammer utstyrt med en omrø-rer av sigmabladtypen. Den termiske spaltningshastighet (målt som foran) var 0,025 vektsprosent i minuttet. Forut for behandlingen var spaltningshastigheten 3,0 vektsprosent i minuttet. Fifty parts of the oxymethylene polymer of Example 1 was milled at 200 to 202°C for 45 minutes with 0.25 parts of 2,2'-methylene-bis-(4-methyl-6-tertiarybutylphenol) and 0.05 parts of "Nalcamine G-13" in a heated chamber equipped with a stirrer of the sigma blade type. The thermal decomposition rate (measured as before) was 0.025 weight percent per minute. Prior to the treatment, the decomposition rate was 3.0% by weight per minute.
Eksempel 17. Example 17.
Eksempel 16 ble gjentatt, bortsett fra at «Nalcamine G-14» ble brukt istedenfor «Nalcamine G-13» på lik vektbasis. Spaltningshastigheten ble redusert til 0,06 vektsprosent i minuttet. Example 16 was repeated, except that "Nalcamine G-14" was used in place of "Nalcamine G-13" on an equal weight basis. The cleavage rate was reduced to 0.06 weight percent per minute.
Oppmalingsoperasj onene i de foranstående eksempler ble gjennomført ved en temperatur på omtrent 200° C. Formalde-hydgass ble avgitt fra polymerene under oppmalingsoperasjonene. The grinding operations in the preceding examples were carried out at a temperature of approximately 200° C. Formaldehyde gas was released from the polymers during the grinding operations.
Alle de foran foretrukne stabilisasjons-systemer er de systemer som anvender trioksan-sampolymerer som inneholder 2 til 10 vektsprosent av enheter oppnådd fra dioksolan, under anvendelse av 0,3 til 1,0 vektsprosent 2,2'-metylen-bis-(4-metyl-6-tertiærbutylfenol) og 0,03 til 0,2 vektsprosent cyanoguanidin eller diallylmelamin. Av det sistnevnte par forbindelser foretrekkes cyanoguanidin. All of the above preferred stabilization systems are those systems using trioxane copolymers containing 2 to 10 percent by weight of units obtained from dioxolane, using 0.3 to 1.0 percent by weight of 2,2'-methylene-bis-(4- methyl-6-tertiarybutylphenol) and 0.03 to 0.2% by weight cyanoguanidine or diallylmelamine. Of the latter pair of compounds, cyanoguanidine is preferred.
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US6242526B1 (en) * | 1997-01-28 | 2001-06-05 | Stepan Company | Antimicrobial polymer latexes derived from unsaturated quaternary ammonium compounds and antimicrobial coatings, sealants, adhesives and elastomers produced from such latexes |
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NL7015362A (en) | 1971-04-22 |
NO139958C (en) | 1979-06-13 |
NL166700B (en) | 1981-04-15 |
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