EP0000371A1 - Powder dispersions in monomer-free unsaturated polyesters and their use as carriers for curable unsaturated polyesters - Google Patents
Powder dispersions in monomer-free unsaturated polyesters and their use as carriers for curable unsaturated polyesters Download PDFInfo
- Publication number
- EP0000371A1 EP0000371A1 EP78100307A EP78100307A EP0000371A1 EP 0000371 A1 EP0000371 A1 EP 0000371A1 EP 78100307 A EP78100307 A EP 78100307A EP 78100307 A EP78100307 A EP 78100307A EP 0000371 A1 EP0000371 A1 EP 0000371A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- unsaturated polyesters
- polyester
- und
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 18
- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 title description 5
- 239000000969 carrier Substances 0.000 title 1
- 239000002253 acid Substances 0.000 claims abstract description 17
- 150000001298 alcohols Chemical class 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 150000002009 diols Chemical class 0.000 claims abstract description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 description 24
- 239000000203 mixture Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 150000003900 succinic acid esters Chemical class 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 229920001225 polyester resin Polymers 0.000 description 12
- 239000004645 polyester resin Substances 0.000 description 12
- -1 chalk Substances 0.000 description 11
- 239000002562 thickening agent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000013008 thixotropic agent Substances 0.000 description 8
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- 239000000049 pigment Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000003903 2-propenyl group Chemical class [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 230000009974 thixotropic effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 2
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N Suberic acid Natural products OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 150000001715 carbamic acids Chemical class 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000000465 moulding Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
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- 238000004062 sedimentation Methods 0.000 description 2
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- 125000003368 amide group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- VLHZUYUOEGBBJB-UHFFFAOYSA-N hydroxy stearic acid Natural products OCCCCCCCCCCCCCCCCCC(O)=O VLHZUYUOEGBBJB-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- JGEMYUOFGVHXKV-UPHRSURJSA-N malealdehyde Chemical compound O=C\C=C/C=O JGEMYUOFGVHXKV-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
Definitions
- the present invention relates to dispersions of powdery substances in unsaturated polyesters which are free from copolymerizable monomers. These dispersions according to the invention are an excellent form in which thickeners, pigments, fillers and other solid auxiliaries can be mixed in finely divided form with unsaturated polyester resins.
- DT-OS 2 223 989 discloses mixtures of inorganic thickeners, ie preferably oxides and hydroxides of the elements of the 2nd and 3rd main groups (groups II a and III a) of the periodic table, and a polyester with acid numbers from 5 to 50 and hydroxyl numbers known from 100 to 300.
- this polyester has a relatively low viscosity, so that it is suitable for absorbing considerable amounts of inorganic thickeners and can serve as the basis for a thickening paste. Since its viscosity hardly increases when thickening agents are added, the thickening pastes made from it can be stored for a long time.
- the pigments have hitherto also been rubbed into the polyester resin used, while other, smaller amounts of solid additives, such as, for example, thickeners, release agents or thixotropic agents, are added as powders.
- solid additives such as, for example, thickeners, release agents or thixotropic agents
- Such pastes are often combined in one or two mixed pastes, since it is easier to precisely dose larger amounts of a paste than small amounts of different pastes.
- These technical requirements mean that the amount of paste base supplied is greater than previously customary. Quantities of 10-15 parts by weight per 100 parts by weight of the polyester resin used are often required. Because of this large amount, customary liquid plasticizers are eliminated, except for the reasons already mentioned, primarily because they do not polymerize when the polyester resin is cured and, as a result, tend to exude. In addition, the mechanical, thermal and electrical properties of the hardening products deteriorate considerably.
- the laminate is generally covered with a colored fine layer. If articles with frequently changing colors are produced in this way, or if colors have to be tinted by adding small amounts of other pigments, it is advantageous to use pigment pastes.
- Plasticizers or styrene-containing polyesters are not suitable as a paste base for the reasons already described. Polyesters according to DF-OS2223989 cannot be used either, because they impair the water absorption of a fine layer so that bubbles and cracks develop after the laminate has been briefly stored in water.
- Another object of the invention is the use of the dispersions according to the invention as auxiliaries for ⁇ , ⁇ -ethylenically unsaturated polyester resins.
- ⁇ , ⁇ -ethylenically unsaturated polyesters are the usual condensation products of at least one ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid with generally 4 or 5 carbon atoms or their ester-forming derivatives, if appropriate in a mixture with up to 100 mol. , based on the unsaturated acid component, at least one aliphatic saturated with 4 to 10 carbon atoms or an aromatic or cycloaliphatic dicarboxylic acid with 8 to 10 carbon atoms or their ester-forming derivatives with at least one polyhydroxy compound, in particular dihydroxy compound, with 2-8 C atoms - that is, polyester, as described in J. Björksen et al, "Polyesters and their Applications", Reinhold Publishing Corp., New York 1956 .
- Examples of preferred unsaturated dicarboxylic acids or their derivatives are maleic anhydride and fumaric acid. Can be used e.g. however also mesaconic acid, citraconic acid, itaconic acid or chloromaleic acid.
- Examples of the aliphatic saturated, aromatic and cycloaliphatic dicarboxylic acids or their derivatives to be used are phthalic acid or phthalic anhydride, isophthalic acid, terephthalic acid, hexa- or tetrahydrophthalic acid or their anhydrides, endomethylene tetrahydrophthalic acid or their anhydride and succinic acid, succinic acid or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or
- polyesters to be used preferably contain maleic acid residues which can be replaced up to 25 mol-96 by phthalic acid or isophthalic acid residues.
- ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,2-butanediol, -1,3, -1,4, -2,3, neopentyl glycol, 1,6-hexanediol , 2,2-bis (4-hydroxycyclohexyl) propane, bis-oxyalkylated bisphenol A, perhydrobisphenol and others can be used.
- Oligomers of ethylene oxide, propylene oxide and butene oxide in particular diethylene glycol, triethylene glycol, tetraethylene glycol and dipropylene glycol, tripropylene glycol and corresponding oligomers of the different butene oxides are preferably used.
- Suitable monohydric alcohols are aliphatic, cycloaliphatic, aromatic and alkylaromatic alcohols with 1 to 18 carbon atoms, e.g. Methanol, ethanol, n- or isopropanol, n-, iso- or tert-butanol, the pentanols, hexanols, heptanols, octanols such as, for example, ⁇ -ethylhexanol, up to long-chain, such as, for example, stearyl alcohol.
- An example of aromatic, monohydric alcohols is benzyl alcohol. Cyclohexanol may be mentioned as an example of cycloaliphatic, monohydric alcohols. Unsaturated monoalcohols, such as allyl alcohol or croton alcohol, can also be used.
- the molecular weights of the polyester B determined as the middle of the number should be between 250 and 3000 (measured by vapor pressure osmometry in dioxane and acetone, with lower values the lower is considered correct, the viscosities of the polyester B between 200 and 1000 cP.
- Powdery substances A include inorganic or organic pigments, thixotropic agents, inorganic thickeners, fillers, etc.
- magnesium hydroxide In addition to magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, zinc oxide, aluminates, titanates, aluminum oxides and their mixed oxides and mixtures of the products mentioned, and Portland cement are also suitable as inorganic thickeners.
- Dispersions of 30 to 60% by weight of oxides and / or hydroxides of the 2nd and 3rd group of the periodic system primarily magnesium oxide and / or magnesium hydroxide, and 70 to 40% by weight of a polyester of maleic acid and have proven to be particularly valuable / or fumaric acid, dipropylene glycol and ol-ethylhexanol proved.
- the dispersions according to the invention can contain further additives, e.g. contain those that affect sedimentation and thixotropy.
- the thixotropy and sedimentation mainly influence inorganic thixotropic agents, such as highly disperse silicas, products with an asbestos-like silicate structure, bentones or organic thixotropic agents, such as hydrogenated castor oil fatty acids, preferably organic compounds containing CONH or OCONH groups.
- organic thixotropic agents which are preferably to be used, can be mixed into the dispersions according to the invention or else incorporated into the polyester B.
- the thixotropic agents can simply be admixed during the preparation of the dispersion according to the invention, but if desired also by condensing in the starting components of the unsaturated polyester B during its production, or condensed therein after the production thereof.
- thixotropic polyesters are e.g. Reaction products which are prepared from unsaturated polyesters containing hydroxyl groups and having a hydroxyl number of 10-80 and an acid number of 1-50 and predominantly reaction products containing a free isocyanate group and consisting of polyisocyanates and monohydroxyl compounds.
- the isocyanates are thixotropic agents which are particularly suitable for incorporation into or for condensing onto unsaturated polyesters B.
- aliphatic, cycloaliphatic and aromatic monoisocyanates with at least 4 carbon atoms such as dodecyl isocyanate, phenyl isocyanate, naphthyl isocyanate, cyclohexyl isocyanate and the C 1 -C 4 alkyl derivatives of the isocyanates mentioned
- diisocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate , 4'-dicyclohexylmethane diisocyanate, 1-methyl-cyclohexane-2,4- and -2,6-diisocyanate and the mixtures of these isomers, 2,4- and 2,6-tolylene diisocyanate and the mixtures of these isomers, naphthylene-1, 5-diisocyanate, 4,4'
- diisocyanates and polyisocyanates are preferred, the functionality of which is achieved by conversion with Zerewitinoff-H-acidic, monofunctional compounds, e.g. monofunctional alcohols and / or acids can be reduced to 2 or 1.
- Thixotropic agents are generally used in amounts of 0.1-10, preferably 1-5% by weight, based on polyester resin.
- the dispersions according to the invention can contain organic and / or inorganic fillers in fibrous and / or powdery form, e.g. Kaolin, magnesium and calcium carbonate, quartz flour, asbestos flour, thermoplastic powder, e.g. Polyethylene powder and other macromolecular cross-linked and non-cross-linked products in powder form.
- Crosslinked macromolecular substances include e.g. considered: ground thermoset plastics, e.g. hardened unsaturated polyester resin, hardened melamine and urea formaldehyde resin.
- Fibrous fillers are e.g. Glass fiber sections, asbestos fibers, "organic chemical fibers" and natural fibers.
- the preferred field of application of the mixtures according to the invention is the use for thickening unsaturated polyester solutions in copolymerizable monomers for the production of resin mats and molding compounds. Since such batches must contain peroxides, preferably organic peroxides, in order to be able to process them into molded parts, it may be expedient to incorporate the organic peroxides into the dispersions according to the invention.
- Peroxides for resin mats and molding compounds are, for example: benzoyl peroxide, tert-butyl perbenzoate, perketals, etc. The perketals are particularly advantageous. They show the greatest storage stability in the presence of basic products.
- the inventive dispersions can be modified unsaturated polyester resins in quantities of 1 - 3 are 0 wt .-%, based on unmodified unsaturated polyester resin admixed. If the dispersions according to the invention contain inorganic thickeners, the Amounts selected so that 0.1 - 10% by weight, preferably 0.5 - 2.5% by weight, based on unsaturated unmodified polyester resin, of inorganic thickeners are added to the unsaturated polyester resins.
- the unsaturated polyesters of those polyester resins for the modification of which the dispersions according to the invention can be used can be prepared from the components listed above for the production of polyester B.
- the acid numbers of the polyesters should be between 10 and 100, preferably between 10 and 40, the OH numbers between 10 and 150, preferably between 20 and 100, and the number average molecular weights between about 500 and 5000, preferably between about 100 and 3,000 (measured by vapor pressure osmometry in dioxane and acetone; if the values differ, the lower one is considered the correct one).
- Suitable copolymerizable vinyl and vinylidene compounds for the modified polyester resins are unsaturated compounds customary in polyester technology, which preferably carry £ -substituted vinyl groups or B-substituted allyl groups, preferably styrene; but also, for example, nuclear chlorinated and alkylated or alkenylated styrenes, where the alkyl groups can contain 1 to 4 carbon atoms, such as vinyltoluene, divinylbenzene, ⁇ -methylstyrene, tert-butylstyrene, chlorostyrenes; Vinyl esters of carboxylic acids with 2-6 carbon atoms, preferably vinyl acetate; Vinyl pyridine, vinyl naphthalene, vinyl cyclohexane, acrylic acid and methacrylic acid and / or their esters (preferably vinyl, allyl and methallyl esters) with 1-4 carbon atoms in the alcohol component, their amines and nitriles
- insoluble is intended to mean that when heated to 80 ° C. for 30 minutes in polyester B, less than 1% by weight of the substance in question goes into solution.
- Resin 1 (comparison according to DT-OS 2 223 989)
- a mixture of 2536 parts of ⁇ -ethylhexanoic acid, 5706 parts of dipropylene glycol and 1738 parts of maleic anhydride, corresponding to a molar composition of 1.0: 2.4: 1.0, are heated in 8 hours to 200 ° C. while passing nitrogen through and at this Temperature until an acid number of 22 and a viscosity of 380 mPa.s. (measured at 20 ° C) kept.
- the product obtained has a hydroxyl number of 200.
- a mixture of 2187 parts of benzyl alcohol, 2633 parts of 2-ethylhexanol-1, 3453 parts of maleic anhydride and 2360 parts of dipropylene glycol, corresponding to a molar ratio of 1.15: 1.15: 2.20: 1.00, are passed through with nitrogen in 14 Heated to 210 ° C and held at this temperature until an acid number of 21 and a viscosity of 320 mPa.s (measured at 20 ° C) was reached. The hydroxyl number is then 40.
- the product has a hydroxyl number of 15.
- Resins 1-4 were mixed with a commercially available polyester resin mixture, which is typical for use in fine layers, according to the following recipe:
- Test specimens (30 ⁇ 100 mm 2 ) were produced from the plates produced according to test A and were stored in distilled water at room temperature for 5 months. The appearance was then assessed.
- a resin mat base was produced according to the following recipe:
- the batch was poured into 3 mm plate molds and allowed to thicken for four days.
- the plates were then cured in a water bath at 75 ° C. for 3 hours and then tempered at 100 ° C. for 15 hours.
- Test specimens 50 x 50 mm 2 ) were cut from the plates and the water absorption was determined according to DIN 53 475. Sheets from a batch containing 100 parts of polyester resin Z without addition of resin served as a comparison.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
α,β-Äthylenisch ungesättigte Polyester aus Dicarbonsäuren, ein- und zweiwertigen Alkoholen mit Säurezahlen von 1-50 und Hydroxylzahlen von 10-80, zu deren Herstellung pro Mol Diole 1,5-2,5 Mol Dicarbonsäuren und 1,5-2,5 Mol einwertiger Alkohole eingesetzt worden sind, eignen sich in hervorragender Weise als Basis für Dispersionen, die pulverige unlösliche Substanzen enthalten.α, β-ethylenically unsaturated polyesters from dicarboxylic acids, mono- and dihydric alcohols with acid numbers of 1-50 and hydroxyl numbers of 10-80, for their production 1.5-2.5 moles of dicarboxylic acids and 1.5-2 per mole of diols, 5 moles of monohydric alcohols have been used as an excellent basis for dispersions containing powdery insoluble substances.
Description
Die vorliegende Erfindung betrifft Dispersionen pulveriger Substanzen in ungesättigten Polyestern, die frei von copolymerisierbaren Monomeren sind. Diese erfindungsgemässen Dispersionen stellen eine ausgezeichnete Form dar, in der Eindickungsmittel, Pigmente, Füllstoffe und andere feste Hilfsmittel in fein verteilter Form ungesättigten Polyesterharzen zugemischt werden können.The present invention relates to dispersions of powdery substances in unsaturated polyesters which are free from copolymerizable monomers. These dispersions according to the invention are an excellent form in which thickeners, pigments, fillers and other solid auxiliaries can be mixed in finely divided form with unsaturated polyester resins.
Aus der DT-OS 2 223 989 sind Gemische aus anorganischen Eindickungsmitteln, also vorzugsweise Oxiden und Hydroxiden der Elemente der 2. und 3. Hauptgruppe (Gruppen II a und III a) des Periodensystems, und eines Polyesters mit Säurezahlen von 5 bis 50 und Hydroxylzahlen von 100 bis 300 bekannt. Durch Einbau von Resten einwertiger Alkohole als Kettenabbrecher besitzt dieser Polyester eine relativ geringe Viskosität, so dass er zur Aufnahme beträchtlicher Mengen anorganischer Eindickungsmittel geeignet ist und als Grundlage für eine Eindickungspaste dienen kann. Da seine Viskosität bei Zusatz von Eindickungsmitteln kaum ansteigt, können die daraus hergestellten Eindickungspasten lange gelagert werden.DT-OS 2 223 989 discloses mixtures of inorganic thickeners, ie preferably oxides and hydroxides of the elements of the 2nd and 3rd main groups (groups II a and III a) of the periodic table, and a polyester with acid numbers from 5 to 50 and hydroxyl numbers known from 100 to 300. By incorporating residues of monohydric alcohols as chain terminators, this polyester has a relatively low viscosity, so that it is suitable for absorbing considerable amounts of inorganic thickeners and can serve as the basis for a thickening paste. Since its viscosity hardly increases when thickening agents are added, the thickening pastes made from it can be stored for a long time.
Solche Gemische gewinnen inzwischen stark an Bedeutung, da bei der Herstellung von Harzmatten das Mischen der Ansätze weitgehend automatisiert worden ist. Dabei wünscht man in der Regel die Mischung kontinuierlich durchzuführen, was voraussetzt, daß die verwendeten festen oder pulverförmigen Zuschlagstoffe, wie Füllstoffe, Pigmente und Eindickungsmittel usw., vorher in einer geeigneten Flüssigkeit angepastet oder - bei höheren Qualitätsanforderungen -auf dem Walzenstuhl angerieben werden. Die Füllstoffe, wie Kreide, Dolomit, Kaolin oder andere, werden, da die Mengen etwa der Menge des Polyesterharzes entsprechen, üblicherweise in diesem angeteigt. Die Pigmente wurden bisher ebenfalls in dem verwendeten Polyesterharz angerieben, während andere, kleinere Mengen fester Zusätze, wie beispielsweise Eindickungsmittel, Trennmittel oder Thixotropiermittel, als Pulver zugegeben werden. Bei kontinuierlichen Mischanlagen ist es aus mischungstechischen Gründen notwendig, alle Bestandteile als Pasten zuzuführen, wobei aus Rationalisierungsgründen ein einheitliches Pastenharz notwendig ist.Mixtures of this type are becoming increasingly important since the mixing of the batches has been largely automated in the production of resin mats. It is usually desirable to carry out the mixing continuously, which presupposes that the solid or powdery additives used, such as fillers, pigments and thickening agents, etc., are previously pasted in a suitable liquid or - in the case of higher quality requirements - rubbed on the roller mill. The fillers, such as chalk, dolomite, kaolin or others, are usually made into a paste since the amounts correspond approximately to the amount of the polyester resin. The pigments have hitherto also been rubbed into the polyester resin used, while other, smaller amounts of solid additives, such as, for example, thickeners, release agents or thixotropic agents, are added as powders. In the case of continuous mixing plants, for technical reasons of mixing it is necessary to supply all the components as pastes, a uniform paste resin being necessary for reasons of rationalization.
Oft werden solche Pasten auch in einer oder zwei Mischpasten vereinigt, da es leichter ist, größere Mengen einer Paste als kleine Mengen verschiedener Pasten kontinuierlich genau zu dosieren. Diese technischen Anforderungen bringen es mit sich, daß die Menge der zugeführten Pastengrundlage größer wird als bisher üblich. Es werden oft Mengen von 10 - 15 Gewichtsteilen auf 100 Gewichtsteile des verwendeten Polyesterharzes benötigt. Wegen dieser großen Menge scheiden übliche, flüssige Weichmacher, außer aus den bereits genannten Gründen, vor allem deswegen aus, weil sie beim Härten des Polyesterharzes nicht mit einpolymerisieren und infolgedessen zum Ausschwitzen neigen. Außerdem werden die mechanischen, thermischen und elektrischen Eigenschaften der Härtungsprodukte erheblich verschlechert.Such pastes are often combined in one or two mixed pastes, since it is easier to precisely dose larger amounts of a paste than small amounts of different pastes. These technical requirements mean that the amount of paste base supplied is greater than previously customary. Quantities of 10-15 parts by weight per 100 parts by weight of the polyester resin used are often required. Because of this large amount, customary liquid plasticizers are eliminated, except for the reasons already mentioned, primarily because they do not polymerize when the polyester resin is cured and, as a result, tend to exude. In addition, the mechanical, thermal and electrical properties of the hardening products deteriorate considerably.
Ubliche, styrolhaltige ungesättigte Polyesterharze sind nicht zu verwenden, da sie zu vorzeitiger Polymerisation neigen. Vor allem bestimmte Pigmentpasten erreichen nicht die gewünschte Lagerstabilität. Gerade bei Pigmentpasten ist es aber vielfach erforderlich, um Farbkonstanz gewährleisten zu können, die Farbpaste für ein gesamtes, sich oft über lange Zeit hinziehendes Lieferprogramm auf einmal anzusetzen.Usual, styrene-containing unsaturated polyester resins should not be used because they tend to polymerize prematurely. Certain pigment pastes in particular do not achieve the desired storage stability. However, in the case of pigment pastes in particular, in order to be able to guarantee color consistency, it is often necessary to apply the color paste at once for an entire delivery program, which often takes a long time.
Bei Verwendung styrolfreier, spezieller ungesättigter Polyester, wie sie in DT-OS 2 223 989 beschrieben sind, zeigt es sich, daß bei Verwendung größerer Mengen die Wasseraufnahme der Preßteile drastisch ansteigt. Dieses Ansteigen ist noch nicht bemerkbar, wenn diese Harze nur in Form von MgO- oder CaO-Pasten den Harzmatten zugesetzt werden, weil in diesem Fall nur 1-3 Gewichteile auf 100 Gewichtsteile Polyesterharz eingesetzt werden. Sobald jedoch, wie oben beschrieben, größere Mengen benötigt werden, ist die Erhöhung der Wasseraufnahme nicht mehr tragbar.When using styrene-free, special unsaturated polyester, as described in DT-OS 2 223 989, it is found that the water absorption of the pressed parts increases drastically when larger amounts are used. This increase is not yet noticeable if these resins are only added to the resin mats in the form of MgO or CaO pastes, because in this case only 1-3 parts by weight are used per 100 parts by weight of polyester resin. However, as soon as larger amounts are required, as described above, the increase in water absorption is no longer acceptable.
Bei Formteilen, die nach einem der üblichen Laminierverfahren hergestellt werden, z.B. bei Booten, ist das Laminat im allgemeinen mit einer eingefärbten Feinschicht bedeckt. Werden auf diese Weise Artikel mit häufig wechselnden Farben hergestellt, oder müssen Farben durch Zugabe geringer Mengen anderer Pigmente abgetönt werden, ist es von Vorteil, Pigmentpasten zu verwenden. Als Pastengrundlage kommen Weichmacher oder styrolhaltige Polyester aus den bereits geschilderten Gründen nicht in Frage. Auch Polyester entsprechend DF-OS2223989 können nicht eingesetzt werden, da sie die Wasseraufnahme einer Feinschicht so verschlechtern, daß nach kurzer Wasserlagerung des Laminats Blasen und Risse entstehen.For molded parts which are manufactured by one of the usual lamination processes, e.g. in boats, the laminate is generally covered with a colored fine layer. If articles with frequently changing colors are produced in this way, or if colors have to be tinted by adding small amounts of other pigments, it is advantageous to use pigment pastes. Plasticizers or styrene-containing polyesters are not suitable as a paste base for the reasons already described. Polyesters according to DF-OS2223989 cannot be used either, because they impair the water absorption of a fine layer so that bubbles and cracks develop after the laminate has been briefly stored in water.
Überraschenderweise wurde nun gefunden, dass sich die oben geschilderten Nachteile durch Verwendung eines Vernetzungsmittel-freien ungesättigten Polyesters mit Säurezahlen von 1-50, vorzugsweise 5-30, und Hydroxylzahlen von 10-80, vorzugsweise 20-50, bei dessen Herstellung pro Mol Diole 1.5-2.5 Mol Dicarbonsäuren und 1.5-2.5 Mol einwertiger Alkohole eingesetzt worden sind, vermeiden lassen.Surprisingly, it has now been found that the disadvantages described above are eliminated by using a crosslinking agent-free unsaturated polyester with acid numbers of 1-50, preferably 5-30, and hydroxyl numbers of 10-80, preferably 20-50, per mole of diols 1.5 -2.5 moles of dicarboxylic acids and 1.5-2.5 moles of monohydric alcohols have been avoided.
Gegenstand der Erfindung sind also Dispersionen, die frei von copolymerisierbaren Monomeren sind, bestehend aus
- A) 10-80, vorzugsweise 30-60, Gew.-% pulvriger, in B unlöslicher Substanzen, und
- B) 90-20, vorzugsweise 70-40 Gew.-% eines α,β-äthylenisch ungesättigten Polyesters aus Dicarbonsäuren, ein- und zweiwertigen Alkoholen,
wobei sich die Prozentangaben jeweils auf die Summe der Komponenten A und B beziehen, dadurch gekennzeichnet, dass der ungesättigte Polyester B Säurezahlen von 1-50 und Hydroxylzahlen von 10-80 besitzt und dass bei seiner Herstellung pro Mol Diole 1.5-2.5 Mol Dicarbonsäuren und 1.5-2.5 Mol einwertiger Alkohole eingesetzt worden sind.The invention therefore relates to dispersions which are free from copolymerizable monomers and consist of
- A) 10-80, preferably 30-60,% by weight of powdery substances insoluble in B, and
- B) 90-20, preferably 70-40% by weight of an α, β-ethylenically unsaturated polyester composed of dicarboxylic acids, mono- and dihydric alcohols,
where the percentages each relate to the sum of components A and B, characterized in that the unsaturated polyester B has acid numbers of 1-50 and hydroxyl numbers of 10-80 and that 1.5-2.5 moles of dicarboxylic acids and 1.5 -2.5 moles of monohydric alcohols have been used.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der erfindungsgemässen Dispersionen als Hilfsmittel für α,β-äthylenisch ungesättigte Polyesterharze.Another object of the invention is the use of the dispersions according to the invention as auxiliaries for α, β-ethylenically unsaturated polyester resins.
α,β-äthylenisch ungesättigte Polyester im Sinne der Erfindung sind die üblichen Kondensationsprodukte mindestens einer α,β-äthylenisch ungesättigten Dicarbonsäure mit in der Regel 4 oder 5 C-Atomen oder deren esterbildenden Derivate, ggf. in Abmischung mit bis zu 100 Mol-", bezogen auf die ungesättigten Säurekomponente ,mindestens einer aliphatischen gesättigten mit 4 - 10 C-Atomen oder einer aromatischen oder cycloaliphatischen Dicarbonsäure mit 8 - 10 C-Atomen oder deren esterbildenden Derivate mit mindestens einer Polyhydroxyverbindung, insbesondere Dihydroxyverbindung, mit 2 - 8 C-Atomen - also Polyester, wie sie bei J. Björksen et al, "Polyesters and their Applications", Reinhold Publishing Corp., New York 1956, beschrieben sind.For the purposes of the invention, α, β-ethylenically unsaturated polyesters are the usual condensation products of at least one α, β-ethylenically unsaturated dicarboxylic acid with generally 4 or 5 carbon atoms or their ester-forming derivatives, if appropriate in a mixture with up to 100 mol. , based on the unsaturated acid component, at least one aliphatic saturated with 4 to 10 carbon atoms or an aromatic or cycloaliphatic dicarboxylic acid with 8 to 10 carbon atoms or their ester-forming derivatives with at least one polyhydroxy compound, in particular dihydroxy compound, with 2-8 C atoms - that is, polyester, as described in J. Björksen et al, "Polyesters and their Applications", Reinhold Publishing Corp., New York 1956 .
Beispiele für bevorzugt zu verwendende ungesättigte Dicarbonsäuren oder ihre Derivate sind Maleinsäureanhydrid und Fumarsäure. Verwendet werden können z.B. jedoch auch Mesaconsäure, Citraconsäure, Itaconsäure oder Chlormaleinsäure. Beispiele für die zu verwendenden aliphatischen gesättigten, aromatischen und cycloaliphatischen Dicarbonsäuren oder ihre Derivate sind Phthalsäure oder Phthalsäureanhydrid, Isophthalsäure, Terephthalsäure, Hexa- oder Tetrahydrophthalsäure bzw. deren Anhydride, Endomethylentetrahydrophthalsäure oder deren Anhydrid, Bernsteinsäure bzw. Bernsteinsäureanhydrid und Bernsteinsäureester und -chloride, Adipinsäure, Sebacinsäure. Um schwerentflammbare Harze herzustellen, können z.B. Hexachlorendomethylentetrahydrophthalsäure (Hetsäure), Tetrachlorphthalsäure oder Tetrabromphthalsäure verwendet werden. Bevorzugt zu verwendende Polyester enthalten Maleinsäurereste, die bis zu 25 Mol-96 durch Phthalsäure- oder Isophthalsäurereste ersetzt werden können. Als zweiwertige Alkohole können Äthylenglykol, Propandiol-1,2, Propandiol-1,3, Diäthylenglykol, Dipropylenglykol, Butandiol-1,2, -1,3, -1,4, -2,3, Neopentylglykol, Hexandiol-1,6, 2,2-Bis (4-hydroxycyclohexyl)-propan, bis-oxalkyliertes Bisphenol A, Perhydrobisphenol und andere eingesetzt werden. Bevorzugt verwendet werden Oligomere von Äthylenoxid, Propylenoxid und Butenoxid, insbesondere Diäthylenglykol, Triäthylenglykol, Tetraäthylenglykol und Dipropylenglykol, Tripropylenglykol sowie entsprechende Oligomere von den verschiedenen Butenoxiden.Examples of preferred unsaturated dicarboxylic acids or their derivatives are maleic anhydride and fumaric acid. Can be used e.g. however also mesaconic acid, citraconic acid, itaconic acid or chloromaleic acid. Examples of the aliphatic saturated, aromatic and cycloaliphatic dicarboxylic acids or their derivatives to be used are phthalic acid or phthalic anhydride, isophthalic acid, terephthalic acid, hexa- or tetrahydrophthalic acid or their anhydrides, endomethylene tetrahydrophthalic acid or their anhydride and succinic acid, succinic acid or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester or succinic acid ester, respectively, Sebacic acid. To make flame retardant resins, e.g. Hexachlorodomethylene tetrahydrophthalic acid (hetic acid), tetrachlorophthalic acid or tetrabromophthalic acid can be used. Polyesters to be used preferably contain maleic acid residues which can be replaced up to 25 mol-96 by phthalic acid or isophthalic acid residues. As dihydric alcohols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,2-butanediol, -1,3, -1,4, -2,3, neopentyl glycol, 1,6-hexanediol , 2,2-bis (4-hydroxycyclohexyl) propane, bis-oxyalkylated bisphenol A, perhydrobisphenol and others can be used. Oligomers of ethylene oxide, propylene oxide and butene oxide, in particular diethylene glycol, triethylene glycol, tetraethylene glycol and dipropylene glycol, tripropylene glycol and corresponding oligomers of the different butene oxides are preferably used.
Weitere Modifikationen sind möglich durch Einbau bis zu 10 Mol-%, bezogen auf die Alkohol- bzw. Säurekomponente, drei- und vierwertiger Alkohole mit 6 - 12 C-Atomen, wie Trimethylolpropan, Glycerin und Pentaerythrit sowie von drei-und vierbasischen Carbonsäuren mit 6 - 12 C-Atomen, wie z.B. Trimellithsäure und Benzoltetracarbonsäure. Jedoch empfiehlt es sich um eine Gelierung und damit eine Viskositätserhöhung des Polyesters zu vermeiden, bei Verwendung von tri- und höherfunktionellen Verbindungen soviel monofunktionelle Ausgangskomponenten einzusetzen, dass pro Mol trifunktionelle Verbindung mindestens ein Mol monofunktionelle Verbindung und pro Mol tetrafunktionelle Verbindung mindestens zwei Mol monofunktionelle Verbindung gewählt werden.Further modifications are possible by incorporation of up to 10 mol%, based on the alcohol or acid component, of trihydric and tetravalent alcohols with 6-12 C atoms, such as trimethylolpropane, glycerol and pentaerythritol, and of three- and four-basic carboxylic acids with 6 - 12 carbon atoms, such as Trimellitic acid and benzene tetracarboxylic acid. However, in order to avoid gelling and thus an increase in the viscosity of the polyester, it is recommended to use so much monofunctional starting components when using trifunctional and higher-functional compounds that at least one mole of monofunctional compound per mole of trifunctional compound and at least two moles of monofunctional compound per mole of tetrafunctional compound become.
Als einwertige Alkohole kommen aliphatische, cycloaliphatische, aromatische und alkylaromatische Alkohole mit 1 - 18 C-Atomen in Betracht, z.B. Methanol, Äthanol, n- oder Isopropanol, n-, Iso- oder tert.-Butanol, die Pentanole, Hexanole, Heptanole, Octanole wie beispielsweise α-Äthylhexanol, bis zu langkettigen,wie beispielsweise Stearylalkohol. Ein Beispiel für aromatische, einwertige Alkohole ist Benzylalkohol. Als Beispiel für cycloaliphatische, einwertige Alkohole sei Cyclohexanol genannt. Auch ungesättigte Monoalkohole,wie beispielsweise Allylalkohol oder Crotonalko- hol,können Verwendung finden.Suitable monohydric alcohols are aliphatic, cycloaliphatic, aromatic and alkylaromatic alcohols with 1 to 18 carbon atoms, e.g. Methanol, ethanol, n- or isopropanol, n-, iso- or tert-butanol, the pentanols, hexanols, heptanols, octanols such as, for example, α-ethylhexanol, up to long-chain, such as, for example, stearyl alcohol. An example of aromatic, monohydric alcohols is benzyl alcohol. Cyclohexanol may be mentioned as an example of cycloaliphatic, monohydric alcohols. Unsaturated monoalcohols, such as allyl alcohol or croton alcohol, can also be used.
Die als Zahlenmitte bestimmten Molekulargewichte der Polyester B sollen zwischen 250 und 3000 liegen (dampfdruckosmometrisch gemessen in Dioxan und Aceton,bei differierenden Werten wird der niedrigere als korrekt angesehen, die Viskositäten der Polyester B zwischen 200 und 1000 cP.The molecular weights of the polyester B determined as the middle of the number should be between 250 and 3000 (measured by vapor pressure osmometry in dioxane and acetone, with lower values the lower is considered correct, the viscosities of the polyester B between 200 and 1000 cP.
Als pulvriger Substanzen A kommen anorganische oder organische Pigmente, Thixotropiermittel, anorganische Eindickungsmittel, Füllstoffe etc. in Frage.Powdery substances A include inorganic or organic pigments, thixotropic agents, inorganic thickeners, fillers, etc.
Als anorganische Eindickungsmittel eignen sich ausser Magnesiumoxid auch Magnesiumhydroxid, Calciumoxid, Calciumhydroxid, Zinkoxid, Aluminate, Titanate, Aluminiumoxide und dessen Mischoxide sowie Mischungen der genannten Produkte, weiterhin Portlandzement. Bevorzugt sind die Oxide und Hydroxide der Elemente der 2. und 3. Hauptgruppe des periodischen Systems, insbesondere Magnesiumoxid.In addition to magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, zinc oxide, aluminates, titanates, aluminum oxides and their mixed oxides and mixtures of the products mentioned, and Portland cement are also suitable as inorganic thickeners. The oxides and hydroxides of the elements of the 2nd and 3rd main group of the periodic system, in particular magnesium oxide, are preferred.
Als besonders wertvoll haben sich Dispersionen aus 30 bis 60 Gew.-% Oxiden und/oder Hydroxiden der 2. und 3. Gruppe des periodischen Systems, vornehmlich Magnesiumoxid und/oder Magnesiumhydroxid, und 70 bis 40 Gew.-% eines Polyesters aus Maleinsäure und/oder Fumarsäure, Dipropylenglykol und ol-Äthylhexanol erwiesen.Dispersions of 30 to 60% by weight of oxides and / or hydroxides of the 2nd and 3rd group of the periodic system, primarily magnesium oxide and / or magnesium hydroxide, and 70 to 40% by weight of a polyester of maleic acid and have proven to be particularly valuable / or fumaric acid, dipropylene glycol and ol-ethylhexanol proved.
Die erfindungsgemässen Dispersionen können ausser Oxiden und/oder Hydroxiden der 2. und 3. Gruppe des periodischen Systems und den genannten speziellen Polyestern weitere Zusatzstoffe, z.B. solche, die die Sedimentation und die Thixotropie beeinflussen, enthalten. Die Thixotropie und Sedimentation beeinflussen vor allem anorganische Thixotropiermittel, wie hochdisperse Kieselsäuren, Produkte mit asbestähnlicher Silicatstruktur, Bentone oder organische Thixotropiermittel, wie hydrierte Rizinusölfettsäuren, vorzugsweiseCONH- oder OCONH-Gruppen enthaltende organische Verbindungen. Diese vorzugsweise zu verwendenden organische Thixotropiermittel können den erfindungsgemässen Dispersionen zugemischt oder aber in die Polyester B eingebaut werden.In addition to oxides and / or hydroxides from the 2nd and 3rd groups of the periodic system and the special polyesters mentioned, the dispersions according to the invention can contain further additives, e.g. contain those that affect sedimentation and thixotropy. The thixotropy and sedimentation mainly influence inorganic thixotropic agents, such as highly disperse silicas, products with an asbestos-like silicate structure, bentones or organic thixotropic agents, such as hydrogenated castor oil fatty acids, preferably organic compounds containing CONH or OCONH groups. These organic thixotropic agents, which are preferably to be used, can be mixed into the dispersions according to the invention or else incorporated into the polyester B.
Die besonders bevorzugten CONH- oder OCONH-Gruppen tragenden organischen Verbindungen sind solche, die z.B. in den DT-AS 1 020 428, 1 106 015, 1 182 816, 1 217 611, 1 273 192, 1 569 331 und 1 745 347 beschrieben sind. Im einzelnen handelt es sich dabei um
- a) modifizierte ungesättigte Polyester, vorzugsweise mit OH-Zahlen über 100 und mit Säurezahlen bis 30, die durch Reaktion von ungesättigten linearen oder verzweigten, hydroxylgruDDenhaltigen Polyestern mit ein- oder mehrwertigen β,α-ungesättigten Ätheralkoholen und Polyisocyanaten erhältlich sind. Als besonders geeignet erweisen sich solche modifizierten ungesättigten Polyester, deren Herstellung in Gegenwart von Sauerstoff vorgenommen worden ist.
- b) Polvesteramide, deren Mischungen aus 3 Gewichtsteilen Polyesteramid und 7 Gewichtsteilen Lackbenzin bei Raumtemperatur inhomogen sind und deren Gehalt an polaren-Gruppen bis zu 35, vorzugsweise 14 - 30, Gew.-% beträgt, wobei unter inhomogenen Mischungen solche verstanden werden, die eine zweite flüssige oder feste Phase aufweisen und infolgedessen gegebenenfalls eine Trübung zeigen. Vorzugsweise werden solche Polyesteramide benutzt, die unter Verwendung von Polycarbonsäuren, Polyaminen mit mindestens zwei primären Aminogruppen und entweder Hydroxycarbonsäuren oder Polyalkoholen oder Aminoalkoholen oder Mischungen dieser Hydroxyverbindungen hergestellt sind. Bevorzugte Polyesteramide weisen ein Amidgruppen/Estergruppen-Verhältnis von 0.1 bis 2.2 und Erweichungspunkte unter 230, insbesondere unter 200°C, auf.
- c) polymere Amide mit einem mittleren Molekulargewicht
M n von 500 - 10 000, die Reste von Monoaminomonocarbonsäuren und/oder Diaminen und Dicarbonsäuren aufweisen und deren an den Carbonamidstickstoffatomen befindliche Wasserstoffatome ganz oder teilweise durch wenigstens 4 C-Atome und wenigstens 1 Oxasauerstoffatom aufweisende Mono- bzw. Polyoxaalkylreste substituiert sind. Beispiele für solche Grundpolymere sind Poly-α-caprolactam und Poly-ω-capryllactam, ferner die Polykondensate aus Tetra-, Hexa-oder Octamethylendiamin und Bernstein-, Adipin-, Kork-oder Sebacinsäure. Durch Oxalkylierung können daraus die thixotropierenden polymeren Amine erhalten werden. - d) Polyurethane mit mittleren Molekulargewichten M von 250 - 5 000, insbesondere von 500 - 3 000, die
- 1. urethanartig verknüpft, Reste zweiwertiger Carbaminsäuren und Reste zweiwertiger Hvdroxvlverbindungen sowie gegebenenfalls zusätzlich Reste tiefer- bzw. höherwertiger Carbaminsäuren und/oder Reste tiefer- bzw. höherwertiger Hydroxylverbindungen aufweisen,
- 2. von äthylenisch ungesättigten Gruppen, Resten mehr als 9 C-Atome aufweisender Fettsäuren, Resten von Addukten aus solchen Fettsäuren sowie Isocyanatgruppen bzw. wie diese reagierende Gruppen frei oder praktisch frei sind, und
- 3. Im Gemisch mit dem zu thixotropierenden ungesättigten Polyesterharz homogene und klare Lösungen bilden.
- e) Cyclohexylamide gesättigter höherer Fettsäuren mit mindestens 10 C-Atomen, wie der Caprinsäure, der Myristinsäure, der Palmitinsäure, der Stearinsäure, der Oxystearinsäure, der Behensäure, oder Mischungen dieser Cyclohexylamide; z.B. sind auch die Cyclohexylamide des sogenannten "Hauptlaufs" der Paraffinoxidation geeignet.
- a) Modified unsaturated polyesters, preferably with OH numbers above 100 and with acid numbers up to 30, which can be obtained by reaction of unsaturated linear or branched, hydroxyl-based polyesters with mono- or polyvalent β, α-unsaturated ether alcohols and polyisocyanates. Modified unsaturated polyesters which have been prepared in the presence of oxygen have proven particularly suitable.
- b) Polvesteramide, mixtures of 3 parts by weight of P olyesteramid and 7 parts by weight of mineral spirits are inhomogeneous at room temperature and whose content of up to 35, preferably 14 at polar groups - 30 wt .-%, wherein these are understood to be inhomogeneous mixtures which have a second liquid or solid phase and consequently may show a cloudiness. Preferably polyester amides are used which are produced using polycarboxylic acids, polyamines with at least two primary amino groups and either hydroxy carboxylic acids or polyalcohols or amino alcohols or mixtures of these hydroxy compounds. Preferred polyester amides have an amide group / ester group ratio of 0.1 to 2.2 and softening points below 230, in particular below 200 ° C.
- c) polymeric amides with an average molecular weight
M n from 500 to 10,000, which contain residues of monoaminomonocarboxylic acids and / or diamines and dicarboxylic acids and whose hydrogen atoms on the carbonamide nitrogen atoms are wholly or partly by at least 4 carbon atoms and at least 1 oxa-oxygen mono- or Polyoxaalkyl residues are substituted. Examples of such base polymers are poly-α-caprolactam and poly-ω-capryllactam, furthermore the polycondensates of tetra-, hexa- or octamethylenediamine and succinic, adipic, cork or sebacic acid. The thixotropic polymeric amines can be obtained therefrom by oxyalkylation. - d) polyurethanes with average molecular weights M of 250-5000, in particular 500-3000, the
- 1. linked urethane-like, residues of dibasic carbamic acids and residues of divalent hydroxyl compounds and, if appropriate, additionally residues of lower or higher-valent carbamic acids and / or residues of lower or higher-valent hydroxyl compounds,
- 2. of ethylenically unsaturated groups, residues of more than 9 carbon atoms of fatty acids, residues of adducts of such fatty acids and isocyanate groups or how these reacting groups are free or practically free, and
- 3. Form homogeneous and clear solutions in a mixture with the unsaturated polyester resin to be thixotroped.
- e) cyclohexylamides of saturated higher fatty acids with at least 10 carbon atoms, such as capric acid, myristic acid, palmitic acid, stearic acid, oxystearic acid, behenic acid, or mixtures of these cyclohexylamides; For example, the cyclohexylamides of the so-called "main run" of paraffin oxidation are also suitable.
Die Thixotropiermittel können bei der Herstellung der erfindungsgemässen Dispersion einfach zugemischt, falls erwünscht jedoch auch durch Verkochen mit den Ausgangskomponenten des ungesättigten Polyesters B bei dessen Herstellung in diesen einkondensiert oder nach dessen Herstellung an diesen ankondensiert werden.The thixotropic agents can simply be admixed during the preparation of the dispersion according to the invention, but if desired also by condensing in the starting components of the unsaturated polyester B during its production, or condensed therein after the production thereof.
Besonders bevorzugte, derart thixotropierte Polyester sind z.B. Umsetzungsprodukte, die aus hydroxylgruppenhaltigen ungesättigten Polyestern mit einer Hydroxylzahl von 10 - 80 und einer Säurezahl von 1 - 50 und überwiegend eine freie Isocyanatgruppe tragenden Umsetzungsprodukten aus Polyisocyanaten und Monohydroxylverbindungen hergestellt werden.Particularly preferred such thixotropic polyesters are e.g. Reaction products which are prepared from unsaturated polyesters containing hydroxyl groups and having a hydroxyl number of 10-80 and an acid number of 1-50 and predominantly reaction products containing a free isocyanate group and consisting of polyisocyanates and monohydroxyl compounds.
Thixotropiermittel, die sich vorzüglich zum Einbau in oder zum Ankondensieren an ungesättigte Polyester B eignen, sind die Isocyanate. Im einzelnen seien aliphatische, cycloaliphatische und aromatische Monoisocyanate mit mindestens 4 C-Atomen, wie z.B. Dodecylisocyanat, Phenylisocyanat, Naphthylisocyanat, Cyclohexylisocyanat sowie die C1 - C4 -Alkylderivate der genannten Isocyanate, Diisocyanate wie z.B. 1,6-Hexamethylendiisocyanat, Isophorondiisocyanat, 4,4'-Dicyclohexylmethandiisocyanat, 1-Methyl-cyclohexan-2,4- und -2,6-diisocyanat sowie die.Gemische dieser Isomeren, 2,4- und 2,6-Toluylendiisocyanat sowie die Gemische dieser Isomeren, Naphthylen-1,5-diisocyanat, 4,4'-Diphenylmethandiisocyanat, Xylylen-1,3- und -1,4-diisocyanat, höhermolekulare Polyisocyanate,wie sie aus Polyisocyanaten und Hydroxylgruppen aufweisenden Verbindungen (vgl. z.B. DT-PS 870, 400 und 909,186) gewonnen werden können, ferner Triisocyanate wie 4,4'-Triphenylmethantriisocyanat und Polyarylpolyalkylenpolyisocyanate, wie sie durch Anilin-Aldehyd-(z.B. Formaldehyd)-Kondensation und anschliessende Phosgenierung erhalten werden, oder di- oder trimerisiertes Toluylendiisocyanat genannt.The isocyanates are thixotropic agents which are particularly suitable for incorporation into or for condensing onto unsaturated polyesters B. Specifically, aliphatic, cycloaliphatic and aromatic monoisocyanates with at least 4 carbon atoms, such as dodecyl isocyanate, phenyl isocyanate, naphthyl isocyanate, cyclohexyl isocyanate and the C 1 -C 4 alkyl derivatives of the isocyanates mentioned, diisocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate , 4'-dicyclohexylmethane diisocyanate, 1-methyl-cyclohexane-2,4- and -2,6-diisocyanate and the mixtures of these isomers, 2,4- and 2,6-tolylene diisocyanate and the mixtures of these isomers, naphthylene-1, 5-diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene-1,3- and -1,4-diisocyanate, higher molecular weight polyisocyanates as obtained from compounds containing polyisocyanates and hydroxyl groups (see, for example, DT-PS 870, 400 and 909.186) can also be triisocyanates such as 4,4'-triphenylmethane triisocyanate and polyaryl polyalkylene polyisocyanates, such as those obtained by aniline-aldehyde (for example formaldehyde) condensation and subsequent phosgenation, or di- or trimerization toluene diisocyanate called.
Von den genannten Polyisocyanaten sind Diisocyanate und Polyisocyanate bevorzugt, deren Funktionalität durch Umsatz mit Zerewitinoff-H-aciden, monofunktionellen Verbindungen z.B. monofunktionellen Alkoholen und/oder Säuren auf 2 oder 1 verringert werden kann.Of the polyisocyanates mentioned, diisocyanates and polyisocyanates are preferred, the functionality of which is achieved by conversion with Zerewitinoff-H-acidic, monofunctional compounds, e.g. monofunctional alcohols and / or acids can be reduced to 2 or 1.
Thixotropiermittel werden in der Regel in Mengen von 0,1-10, vorzugsweise 1-5 Gew.-%, bezogen auf Polyesterharz, eingesetzt.Thixotropic agents are generally used in amounts of 0.1-10, preferably 1-5% by weight, based on polyester resin.
Weiterhin können die erfindungsgemässen Dispersionen organische und/oder anorganische Füllstoffe in fasriger und/oder pulvriger Form enthalten, z.B. Kaolin, Magnesium- und Calciumcarbonat, Quarzmehl, Asbestmehl, Thermoplastenpulver, z.B. Polyäthylenpulver und andere makromolekulare vernetzte und nicht vernetzte Produkte in Pulverform. Als vernetzte makromolekulare Substanzen kommen z.B. in Betracht: gemahlene duromere Kunststoffe, z.B. gehärtetes ungesättigtes Polyesterharz, gehärtetes Melamin- und Harnstoff-FormaldehydHarz. Fasrige Füllstoffe sind z.B. Glasfaserabschnitte, Asbestfasern, "organische Chemiefasern" und Naturfasern.Furthermore, the dispersions according to the invention can contain organic and / or inorganic fillers in fibrous and / or powdery form, e.g. Kaolin, magnesium and calcium carbonate, quartz flour, asbestos flour, thermoplastic powder, e.g. Polyethylene powder and other macromolecular cross-linked and non-cross-linked products in powder form. Crosslinked macromolecular substances include e.g. considered: ground thermoset plastics, e.g. hardened unsaturated polyester resin, hardened melamine and urea formaldehyde resin. Fibrous fillers are e.g. Glass fiber sections, asbestos fibers, "organic chemical fibers" and natural fibers.
Bevorzugtes Anwendungsgebiet der erfindungsgemässen Gemische ist die Verwendung zur Eindickung von ungesättigten Polyester-Lösungen in copolymerisierbaren Monomeren zur Herstellung von Harzmatten und Pressmassen. Da derartige Ansätze Peroxide, bevorzugt organische Peroxide, enthalten müssen, um diese zu Formteilen verarbeiten zu können, kann es zweckmässig sein, die organischen Peroxide bereits in die erfindungsgemässen Dispersionen einzuarbeiten. Als Peroxide für Harzmatten und Pressmassen kommen beispielsweise in Betracht: Benzoylperoxid, tert.-Butylperbenzoat, Perketale usw. Besonders vorteilhaft sind die Perketale. Sie zeigen die grösste Lagerstabilität in Gegenwart basischer Produkte.The preferred field of application of the mixtures according to the invention is the use for thickening unsaturated polyester solutions in copolymerizable monomers for the production of resin mats and molding compounds. Since such batches must contain peroxides, preferably organic peroxides, in order to be able to process them into molded parts, it may be expedient to incorporate the organic peroxides into the dispersions according to the invention. Peroxides for resin mats and molding compounds are, for example: benzoyl peroxide, tert-butyl perbenzoate, perketals, etc. The perketals are particularly advantageous. They show the greatest storage stability in the presence of basic products.
Die erfindungsgemässen Dispersionen können den zu modifizierenden ungesättigten Polyesterharzen in Mengen von 1 - 30 Gew.-%, bezogen auf ungesättigtes unmodifiziertes Polyesterharz, zugemischt werden. Enthalten die erfindungsgemässen Dispersionen anorganische Eindickungsmittel, so werden die Mengen so gewählt, dass den ungesättigten Polyesterharzen 0,1 - 10 Gew.-%, vorzugsweise 0,5 - 2,5 Gew.-%, bezogen auf ungesättigtes unmodifiziertes Polyesterharz, anorganischer Eindickungsmittel zugesetzt werden.The inventive dispersions can be modified unsaturated polyester resins in quantities of 1 - 3 are 0 wt .-%, based on unmodified unsaturated polyester resin admixed. If the dispersions according to the invention contain inorganic thickeners, the Amounts selected so that 0.1 - 10% by weight, preferably 0.5 - 2.5% by weight, based on unsaturated unmodified polyester resin, of inorganic thickeners are added to the unsaturated polyester resins.
Die ungesättigten Polyester derjenigen Polyesterharze, zu deren Modifizierung die erfindungsgemässen Dispersionen eingesetzt werden können, können aus den oben für die Herstellung des Polyesters B aufgezählten Komponenten hergestellt werden.The unsaturated polyesters of those polyester resins for the modification of which the dispersions according to the invention can be used can be prepared from the components listed above for the production of polyester B.
Die Säurezahlen der Polyester sollen zwischen 10 und 100, vorzugsweise zwischen 10 und 40, die OH-Zahlen zwischen 10 und 150, vorzugsweise zwischen 20 und 100, und die als Zahlenmittel gemessenen Molekulargewichte zwischen ca. 500 und 5000, vorzugsweise zwischen ca. 100 und 3 000 liegen (dampfdruckosmometrisch gemessen in Dioxan und Aceton; bei differierenden Werten wird der niedrigere als der korrekte angesehen).The acid numbers of the polyesters should be between 10 and 100, preferably between 10 and 40, the OH numbers between 10 and 150, preferably between 20 and 100, and the number average molecular weights between about 500 and 5000, preferably between about 100 and 3,000 (measured by vapor pressure osmometry in dioxane and acetone; if the values differ, the lower one is considered the correct one).
Als copolymerisierbare Vinyl- und Vinylidenverbindungen für die modifizierten Polyesterharze eignen sich in der Polyestertechnologie gebräuchliche ungesättigte Verbindungen, die bevorzugt£-substituierte Vinylgruppen oder B-substituierte Allylgruppen tragen, bevorzugt Styrol; aber auch beispielsweise kernchlorierte und -alkylierte bzw. -alkenylierte Styrole, wobei die Alkylgruppen 1 - 4 Kohlenstoffatome enthalten können, wie z.B. Vinyltoluol, Divinylbenzol, α-Methylstyrol, tert.-Butylstyrol, Chlorstyrole; Vinylester von Carbonsäuren mit 2 - 6 Kohlenstoffatomen, bevorzugt Vinylacetat; Vinylpyridin, Vinylnaphthalin, Vinylcyclohexan, Acrylsäure und Methacrylsäure und/oder ihre Ester (vorzugsweise Vinyl-, Allyl- und Methallylester) mit 1 - 4 Kohlenstoffatomen in der Alkoholkomponente, ihre Amine und Nitrile, Maleinsäureanhydrid, -halb- und diester mit 1 - 4 Kohlenstoffatomen in der Alkoholkomponente, -halb- und -diamine oder cyclische Imide wie N-Methylmaleinimid oder N-Cyclohexylmaleinimid; Allylverbindungen wie Allylbenzol und Allylester wie Allylacetat, Phthalsäurediallylester, Isophthalsäurediallylester, Fumarsäurediallylester, Allylcarbonate, Diallylcarbonate, Triallylphosphat und Triallylcyanurat. Diese Monomeren sind dieselben, von denen die erfindungsgemässen Dispersionen frei sein sollen.Suitable copolymerizable vinyl and vinylidene compounds for the modified polyester resins are unsaturated compounds customary in polyester technology, which preferably carry £ -substituted vinyl groups or B-substituted allyl groups, preferably styrene; but also, for example, nuclear chlorinated and alkylated or alkenylated styrenes, where the alkyl groups can contain 1 to 4 carbon atoms, such as vinyltoluene, divinylbenzene, α-methylstyrene, tert-butylstyrene, chlorostyrenes; Vinyl esters of carboxylic acids with 2-6 carbon atoms, preferably vinyl acetate; Vinyl pyridine, vinyl naphthalene, vinyl cyclohexane, acrylic acid and methacrylic acid and / or their esters (preferably vinyl, allyl and methallyl esters) with 1-4 carbon atoms in the alcohol component, their amines and nitriles, maleic acid hydride, half and diesters with 1-4 carbon atoms in the alcohol component, half and diamines or cyclic imides such as N-methylmaleinimide or N-cyclohexylmaleinimide; Allyl compounds such as allylbenzene and allyl esters such as allyl acetate, diallyl phthalate, diallyisophthalate, diallyl fumarate, allyl carbonates, diallyl carbonates, triallyl phosphate and triallyl cyanurate. These monomers are the same from which the dispersions according to the invention should be free.
"Unlöslich" soll in der vorliegenden Erfindung bedeuten, dass bei 30-minütigem Erhitzen auf 80°C im Polyester B weniger als 1 Gew.-% der fraglichen Substanz in Lösung gehen.In the present invention, “insoluble” is intended to mean that when heated to 80 ° C. for 30 minutes in polyester B, less than 1% by weight of the substance in question goes into solution.
Die in den nachfolgenden Beispielen genannten Prozente bedeuten Gewichtsprozente, Teile sind Gewichtsteile.The percentages given in the examples below mean percentages by weight, parts are parts by weight.
Ein Gemisch aus 2536 Teilen α-Äthylhexansäure, 5706 Teilen Dipropylenglykol und 1738 Teilen Maleinsäureanhydrid, entsprechend einer molaren Zusammensetzung von 1,0 : 2,4 : 1,0 werden in 8 Std. auf 200°C unter Durchleiten von Stickstoff aufgeheizt und bei dieser Temperatur bis zum Erreichen einer Säurezahl von 22 und einer Viskosität von 380 mPa.s. (bei 20°C gemessen) gehalten. Das erhaltene Produkt hat eine Hydroxylzahl von 200.A mixture of 2536 parts of α-ethylhexanoic acid, 5706 parts of dipropylene glycol and 1738 parts of maleic anhydride, corresponding to a molar composition of 1.0: 2.4: 1.0, are heated in 8 hours to 200 ° C. while passing nitrogen through and at this Temperature until an acid number of 22 and a viscosity of 380 mPa.s. (measured at 20 ° C) kept. The product obtained has a hydroxyl number of 200.
Ein Gemisch aus 2187 Teilen Benzylalkohol, 2633 Teilen 2- Äthylhexanol-1, 3453 Teilen Maleinsäureanhydrid und 2360 Teilen Dipropylenglykol entsprechend einem Mol-Verhältnis von 1,15 : 1,15 : 2,20 : 1,00 werden unter Durchleiten von Stickstoff in 14 Std. auf 210°C aufgeheizt und bei dieser Temperatur bis zum Erreichen einer Säurezahl von 21 und einer Viskosität von 320 mPa.s (bei 20°C gemessen) gehalten. Die Hydroxyzahl beträgt dann 40.A mixture of 2187 parts of benzyl alcohol, 2633 parts of 2-ethylhexanol-1, 3453 parts of maleic anhydride and 2360 parts of dipropylene glycol, corresponding to a molar ratio of 1.15: 1.15: 2.20: 1.00, are passed through with nitrogen in 14 Heated to 210 ° C and held at this temperature until an acid number of 21 and a viscosity of 320 mPa.s (measured at 20 ° C) was reached. The hydroxyl number is then 40.
Ein Gemisch aus 9140 Teilen Benzylalkohol, 10 998 Teilen 2-Äthylhexanol-1, 16 583 Teilen Maleinsäureanhydrid und 11 331 Teilen Dipropylenglykol entsprechend einem Molverhältnis von 1,0 : 1,0 : 2,0 : 1,0 wird nach Zusatz von 4,5 Teilen Hydrochinon in 7 Std. auf 220°C aufgeheizt und unter Durchleiten von Stickstoff bei dieser Temperatur bis zu einer Säurezahl von 21 und einer Viskosität von 710 mPa..s (bei 200C gemessen) gehalten. Das Produkt hat eine Hydroxylzahl von 15.A mixture of 9140 parts of benzyl alcohol, 10 998 parts of 2-ethylhexanol-1, 16 583 parts of maleic anhydride and 11 331 parts of dipropylene glycol, corresponding to a molar ratio of 1.0: 1.0: 2.0: 1.0, is added after adding 4. 5 parts of hydroquinone in 7 hrs. heated to 220 ° C and (measured at 20 0 C) while passing nitrogen at this temperature until an acid number of 21 and a viscosity of 710 mPa..s maintained. The product has a hydroxyl number of 15.
Zu 571 Teilen Toluylendiisocyanat (Gemisch aus den 2,4-und 2,6-Isomeren)werden 247 Teile Isopropanol (Molverhältnis 1,05 : 1,0) so zugegeben, dass eine Temperatur von 75°C nicht überschritten wird. Die Reaktion wird fortgeführt, bis der NCO-Gehalt unter 19 % beträgt.247 parts of isopropanol (molar ratio 1.05: 1.0) are added to 571 parts of tolylene diisocyanate (mixture of the 2,4- and 2,6-isomers) in such a way that a temperature of 75 ° C. is not exceeded. The reaction is continued until the NCO content is below 19%.
2 Teile dieses so erhaltenen Thixotropierträgers werden zu 120 Teilen des nach Beispiel 2 erhaltenen Polyesters gegeben und 3 Std. bei 120°C zur Reaktion gebracht. Dabei steigt die Viskosität auf 410 mPa.s.2 parts of the thixotropic carrier thus obtained are added to 120 parts of the polyester obtained according to Example 2 and reacted at 120 ° C. for 3 hours. The viscosity increases to 410 mPa.s.
Mit den Harzen 1 bis 4 wurden folgende Versuche durchgeführt:The following tests were carried out with resins 1 to 4:
Die Harze 1 - 4 wurden mit einem handelsüblichen Polyesterharzgemisch, das typisch für die Verwendung in Feinschichten ist, nach folgender Rezeptur gemischt:
Aus dem Harzgemisch wurden Gießplatten (3 mm dick) hergestellt, die bei 750C 3 Std. gehärtet und 15 Std. bei 100°C getempert wurden. Aus diesen Gießplatten wurden Prüfkörper (50 x 50 mm2) geschnitten, die in destilliertem Wasser bei Raumtemperatur 50 Tage gelagert wurden. Danach wurde die Wasseraufnahme gemäss DIN 53 475 bestimmt.Pour plates (3 mm thick) were made of the resin mixture prepared containing 3 h at 75 0 C. Hardened and annealed for 15 h. At 100 ° C. Test specimens (50 × 50 mm 2 ) were cut from these casting plates and were stored in distilled water at room temperature for 50 days. The water absorption was then determined in accordance with DIN 53 475.
Als Vergleich dienten Platten, die aus einem Harzgemisch gemäss folgender Rezeptur hergestellt wurden:
Aus den gemäss Versuch A hergestellten Platten wurden Prüfkörper (30 x 100 mm2) hergestellt, die 5 Monate in destilliertem Wasser bei Raumtemperatur gelagert wurden. Danach wurde das Aussehen beurteilt.
Nach folgender Rezeptur wurde ein Harzmattenansatz hergestellt:
Der Ansatz wurde in 3-mm-Plattenformen gegossen und vier Tage eindicken gelassen. Danach wurden die Platten bei 75°C 3 Std. im Wasserbad gehärtet und dann 15 Std. bei 100°C getempert. Aus den Platten wurden Prüfkörper (50 x 50 mm2) geschnitten und daran die Wasseraufnahme nach DIN 53 475 bestimmt. Als Vergleich dienten Platten aus einem Ansatz, der 100 Teile Polyesterharz Z ohne Harzzusatz enthielt.The batch was poured into 3 mm plate molds and allowed to thicken for four days. The plates were then cured in a water bath at 75 ° C. for 3 hours and then tempered at 100 ° C. for 15 hours. Test specimens (50 x 50 mm 2 ) were cut from the plates and the water absorption was determined according to DIN 53 475. Sheets from a batch containing 100 parts of polyester resin Z without addition of resin served as a comparison.
Claims (2)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772731320 DE2731320A1 (en) | 1977-07-12 | 1977-07-12 | DISPERSIONS OF POWDERS IN UNSATURATED POLYESTERS |
DE2731320 | 1977-07-12 |
Publications (2)
Publication Number | Publication Date |
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EP0000371A1 true EP0000371A1 (en) | 1979-01-24 |
EP0000371B1 EP0000371B1 (en) | 1980-06-25 |
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ID=6013677
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Application Number | Title | Priority Date | Filing Date |
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EP78100307A Expired EP0000371B1 (en) | 1977-07-12 | 1978-07-05 | Powder dispersions in monomer-free unsaturated polyesters and their use as carriers for curable unsaturated polyesters |
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Country | Link |
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US (1) | US4222927A (en) |
EP (1) | EP0000371B1 (en) |
DE (2) | DE2731320A1 (en) |
ES (1) | ES471653A1 (en) |
IT (1) | IT1105747B (en) |
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DE3126862A1 (en) * | 1981-07-08 | 1983-01-27 | Chemische Werke Hüls AG, 4370 Marl | THICKENING PASTE FOR THE PRODUCTION OF MOLDING MATERIALS THAT ARE HEAT-RESISTABLE, BASED ON UNSATURATED POLYESTER RESIN |
US5244985A (en) * | 1991-03-29 | 1993-09-14 | New Japan Chemical Co., Ltd. | Epoxidized polyesters and method of production thereof |
GB9601589D0 (en) * | 1996-01-26 | 1996-03-27 | Queensway Expert Developments | Polyol compositions for polyurethanes |
GB2340838B (en) * | 1998-08-21 | 2002-02-13 | Cray Valley Ltd | Resins and composites containing them |
US6887832B2 (en) * | 2000-12-29 | 2005-05-03 | Halliburton Energy Service,S Inc. | Method of formulating and using a drilling mud with fragile gels |
US7456135B2 (en) * | 2000-12-29 | 2008-11-25 | Halliburton Energy Services, Inc. | Methods of drilling using flat rheology drilling fluids |
US7572755B2 (en) * | 2000-12-29 | 2009-08-11 | Halliburton Energy Services, Inc. | Drilling fluid comprising a vinyl neodecanoate polymer and method for enhanced suspension |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2628209A (en) * | 1947-10-28 | 1953-02-10 | Us Rubber Co | Process for increasing viscosity of uncured alkyd copolymer resinous mixtures and product |
DE2223989A1 (en) * | 1972-05-17 | 1973-12-06 | Bayer Ag | DISPERSE (COLLOIDS) MIXTURES |
FR2207877A1 (en) * | 1972-11-29 | 1974-06-21 | Kao Corp |
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US2407479A (en) * | 1939-10-31 | 1946-09-10 | Gen Electric | Interpolymerization products |
US2388319A (en) * | 1941-07-11 | 1945-11-06 | Bell Telephone Labor Inc | Cross-linked polyesters and electrical conductors containing them |
US2623025A (en) * | 1949-02-11 | 1952-12-23 | Libbey Owens Ford Glass Co | Production of stable thermosetting compositions |
US3361705A (en) * | 1965-08-03 | 1968-01-02 | Pfizer & Co C | Masterbatch compositions |
US3795650A (en) * | 1972-10-16 | 1974-03-05 | Engelhard Min & Chem | Clay thixotrope for polyester resins and use thereof |
-
1977
- 1977-07-12 DE DE19772731320 patent/DE2731320A1/en not_active Withdrawn
-
1978
- 1978-07-05 DE DE7878100307T patent/DE2860028D1/en not_active Expired
- 1978-07-05 EP EP78100307A patent/EP0000371B1/en not_active Expired
- 1978-07-06 US US05/922,273 patent/US4222927A/en not_active Expired - Lifetime
- 1978-07-10 IT IT50226/78A patent/IT1105747B/en active
- 1978-07-12 ES ES471653A patent/ES471653A1/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2628209A (en) * | 1947-10-28 | 1953-02-10 | Us Rubber Co | Process for increasing viscosity of uncured alkyd copolymer resinous mixtures and product |
DE2223989A1 (en) * | 1972-05-17 | 1973-12-06 | Bayer Ag | DISPERSE (COLLOIDS) MIXTURES |
FR2207877A1 (en) * | 1972-11-29 | 1974-06-21 | Kao Corp |
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US4222927A (en) | 1980-09-16 |
ES471653A1 (en) | 1979-10-01 |
EP0000371B1 (en) | 1980-06-25 |
IT1105747B (en) | 1985-11-04 |
DE2731320A1 (en) | 1979-01-25 |
IT7850226A0 (en) | 1978-07-10 |
DE2860028D1 (en) | 1980-10-30 |
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