CN1234043A - 酸官能化和环氧官能化聚酯树脂 - Google Patents
酸官能化和环氧官能化聚酯树脂 Download PDFInfo
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- CN1234043A CN1234043A CN97199066A CN97199066A CN1234043A CN 1234043 A CN1234043 A CN 1234043A CN 97199066 A CN97199066 A CN 97199066A CN 97199066 A CN97199066 A CN 97199066A CN 1234043 A CN1234043 A CN 1234043A
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- Prior art keywords
- acid
- glycidyl ester
- aliphatic
- uncle
- carbon atoms
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- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 25
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- 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 abstract 2
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
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- 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 3
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- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- HIMXAERGQMNODV-UHFFFAOYSA-N 2-N,4-N,1,2,3,4-hexamethoxy-2-N-methyl-1,3,5-triazine-2,4,6-triamine Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(C)OC)OC)OC)OC HIMXAERGQMNODV-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- 231100000148 Ames mutagenicity Toxicity 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- 238000001838 alkalimetric titration Methods 0.000 description 1
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- 230000001680 brushing effect Effects 0.000 description 1
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- 229930008380 camphor Natural products 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31794—Of cross-linked polyester
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
- Polyesters Or Polycarbonates (AREA)
- Materials For Photolithography (AREA)
Abstract
由下列组分反应得到的线性、叔羧基官能化聚酯树脂a)至少一种化合物A1,包含下面的反应产物(i)式(Ⅰ)的合成高支化饱和单羧酸异构体的混合物的缩水甘油酯:其中R1、R2和R3是1~15个碳原子的烷基,这其中至少一个是甲基,每一种酸含有5~19、优选5~13个碳原子,且优选CARDURA缩水甘油酯,和(ii)该合成高支化饱和单羧酸的混合物,组分(i)和(ii)的摩尔比为1∶1,该组分A1视具体情况而定与羟基新戊酸(A2)和/或氢化二羟苯基丙烷(A3)混合;b)至少一种包含两个芳族或仲脂族羧基的芳族或脂环族二羧酸化合物B或其酐;视具体情况而定c)至少一种包含一个叔脂族羧基和两个脂族羟基的二羟基单羧酸化合物C,其中每一羟基独立地是伯或仲羟基;和d)视具体情况而定至少一种包含两个脂族羟基的二醇化合物D,其中每一羟基独立地是伯或仲羟基;化合物A1∶A2+A∶B∶C∶D的摩尔比是A1∶(2-A1) ∶X+Y+1∶X∶Y,其中A1的范围是0.1~2,Y的范围是0~6,X的范围是2~8,温度是100~225℃,直到基本上所有的在反应混合物中起始存在的非叔羧基已经反应为止;由该聚酯树脂得到的聚缩水甘油酯和包含至少一种聚酯树脂和/或至少一种聚缩水甘油树脂的涂料组合物。
Description
本发明涉及线性叔羧基官能化聚酯树脂、该树脂的制备方法、可通过将该线性叔羧基官能化聚酯树脂缩水甘油化得到的聚缩水甘油酯树脂、包含该线性叔羧基官能化聚酯树脂或该聚缩水甘油酯树脂的涂料组合物、特别是粉末涂料组合物或液体涂料组合物和通过使用所述涂料组合物得到的固化产物。
基于2,2-双(4-羟基苯基)丙烷和表氯醇的固体反应产物的粉末涂料组合物已经公知了很长一段时间。以这些组合物为基础制备的固化产物是耐水解的,然而它们却显示出低的耐紫外线能力,因而不适合于要求高度的室外耐久性的应用例如建筑元件或汽车面漆。
欧洲专利申请447360(EP-A-447,360)中公开了能够用于高质量室外耐久性涂料和模塑组合物中的三缩水甘油酯。由于在三羧酸加合物前体中存在的端羧基官能团的次要性能,因此在这些三羧酸加合物的缩水甘油化过程中应该避免强碱性条件,以免所形成的缩水甘油酯的水解和/或树脂骨架中一种或多种酯基的水解。结果是制得的三缩水甘油酯将含有相对高量的可水解氯和/或含有可能导致毒性问题的低分子量水解产物。
在EP-A-447,360的实施例2中反映出高含量的可水解氯,该申请涉及六氢化邻苯二甲酸酐和二羟甲基丙酸的2∶1加合物的缩水甘油化过程。得到的产物具有氯含量为1.5%。涂料组合物中如此高含量的残余氯一般是不合适的。另外,由于EP-A-447,360中报道的三缩水甘油酯是液体的事实,因此它们不能应用于粉末涂料组合物。
最常用的室外耐久性粉末涂料体系是聚酯/三缩水甘油基异氰脲酸酯(TGIC)。而鉴于健康和安全的原因,人们对TGIC的用途持怀疑的态度。TGIC是比较有毒性的(老鼠口服LD50为0.4g/kg),且根据Ames诱变性试验有迹象表明该化合物是诱变的。
另一方面具有5~13个碳原子的高度支化羧酸的缩水甘油酯CARDURA(商标)公知能够容易地制备和反应,但是其仍然是单官能试剂。
由欧洲专利申请EP0634434A2可知线性叔脂族羧基官能化聚酯树脂的制备方法,其中包括使下列组分反应:(a)至少一种包含一个单官能伯或仲羟基的化合物A′和/或至少一种包含一个伯或仲羟基和一个叔脂族羧基的化合物A″;(b)至少一种包含两个芳族或仲脂族羧基的芳族或脂环族二羧酸化合物B或其酐;(c)至少一种包含两个脂族羟基的二醇化合物C,其中羟基可以独立地是伯或仲羟基;和(d)至少一种包含一个叔脂族羧基和两个脂族羟基的二羟基单羧酸化合物D,其中每一羟基可以独立地是伯或仲羟基,化合物A′∶A″∶B∶C∶D的摩尔比是M∶N∶X+Y+1∶X∶Y,其中M+N=2,X范围是2~8,Y范围是2-N~8,温度是100~240℃,直到基本上所有的在反应混合物中起始存在的非叔羧基全部反应为止。
该申请中公开了在合适的碱和催化剂存在下,由该线性叔脂族羧基官能化聚酯与过量表卤醇反应得到的聚缩水甘油酯树脂。优选地,聚酯与表氯醇反应。所述的线性聚酯和由此得到的相应聚缩水甘油酯与交联剂一起用于粉末涂料组合物中。
欧洲专利申请EP0720997A2披露了线性叔羧基官能化聚酯和环氧官能化聚酯树脂。这些聚酯树脂由以下反应得到:a)至少一种包含两个芳族和/或仲脂族羧基的芳族和/或脂环族羧酸化合物A或其酐,b)至少一种包含两个脂族羟基的羟基化合物B,其中每一羟基可以独立地是伯或仲羟基,c)至少一种包含至少一个叔脂族羧基和两个脂族羟基的羟基取代羧酸化合物C,其中每一羟基可以独立地是伯或仲羟基,和d)视具体情况而存在的一种包含一个羧基的羧酸化合物D,化合物A∶B∶C∶D的摩尔比是(X+Y-1)∶X∶Y∶Z,其中X范围是2~8,Y范围是2~8,Z范围是0~2。
这些聚酯树脂能够与合适的固化剂一起用于粉末涂料的生产,或者能够转变成相应的缩水甘油酯,再与合适的固化剂一起用于粉末涂料的生产。
虽然按照优异的室外耐久性(UV稳定性)和固化状态下的耐水解性的要求,线性叔脂族羧基官能化聚酯树脂和其聚缩水甘油酯能够实现一定程度的进步,但是就它们在以现代化方式经济地施用的粉末涂料中的应用来说,仍需进一步改进这些性能。
因此,本发明的目的是提供线性、酸官能化聚酯树脂,其中酸官能度仅包含叔脂族羧酸官能度,该聚酯树脂能够容易地被缩水甘油化以形成聚缩水甘油酯树脂。当用于室外可耐久的粉末涂料组合物中时,该线性、叔羧基官能化聚酯树脂和该聚缩水甘油酯树脂必需显示进一步改进的性能,其对环境是相对友好的。
由于大量的研究和实验,目前已经惊人地发现了所研究的该线性酸官能化聚酯树脂。
因此,本发明提供由下面的反应得到的线性、叔羧基官能化聚酯树脂a)至少一种化合物A1,包含下列组分的反应产物(ⅰ)下式的合成高支化饱和单羧酸异构体的混合物的缩水甘油酯:,其中R1、R2和R3是1~15个碳原子的烷基,这其中至少一个是甲基,每一种酸含有5~19、优选5~13个碳原子,且优选CARDURA缩水甘油酯,和(ⅱ)该合成高支化饱和单羧酸的混合物,组分(ⅰ)和(ⅱ)的摩尔比为1∶1,该组分A1视具体情况而定与羟基新戊酸(A2)和/或氢化二羟苯基丙烷(A3)混合;b)至少一种包含两个芳族或仲脂族羧基的芳族或脂环族二羧酸化合物B或其酐;以及视具体情况而存在的c)至少一种包含一个叔脂族羧基和两个脂族羟基的二羟基单羧酸化合物C,其中每一羟基独立地是伯或仲羟基;和d)视具体情况而定至少一种包含两个脂族羟基的二醇化合物D,其中每一羟基独立地是伯或仲羟基;
化合物A1∶A2+A3∶B∶C∶D的摩尔比是A1∶(2-A1)∶X+Y+1∶X∶Y,其中A1范围是0.1~2,Y范围是0~6,X范围是2~8,温度是100~225℃,直到基本上所有的在反应混合物中起始存在的非叔羧基全部反应为止。
当其酸值实际上相当于理论酸值时,其中理论酸值根据反应混合物中起始存在的反应物的叔羧基的量而计算,由此制得的线性叔脂族羧基官能化聚酯树脂基本上不含有非叔羧基。术语“实际上”此处用来表示与理论值存在至多+/-5%、优选至多3%的偏差。这由标准碱量滴定法测定。
对于本领域熟练人员来说应该明白,所制得树脂的分子量分布和数均分子量将取决于本发明方法中的具体反应物和所用比例。虽然在所用酯化反应条件下,化合物A1、A2、A3和D中的叔脂族羧基不反应,但这些叔脂族羧基与表卤醇的缩水甘油化能够在标准碱性条件下进行,于是能够得到聚缩水甘油酯树脂,其含有低的可水解卤素含量,通常低于基于组合物总重量的0.5wt%。
可以理解的是,本发明的其它方面由以下构成:上述线性羧基官能化聚酯的聚缩水甘油酯;包含该线性叔羧基官能化聚酯树脂和/或由此得到的该聚缩水甘油酯的涂料组合物、特别是粉末涂料组合物或液体涂料;和通过使用这些涂料组合物得到的固化产物。
线性叔脂族羧基官能化聚酯的制备方法一般按照通用酯化反应方法、优选按照共沸缩合方法进行。特别地,缩合反应如下进行:将化合物A~D同时加入反应器中,此后在3~8小时的时间内温度由室温升高到180~210℃,于是在连续共沸除去水的条件下启动并进行反应。一般持续进行共沸除水,直到得到其酸值相当于上述理论酸值的反应产物为止。本领域公知的酯化反应催化剂例如二丁基锡氧化物、对甲苯磺酸、辛酸锡、辛酸锌和蓖麻醇酸锂可以用于该酯化方法,但是一般并不需要。
用作本发明线性叔脂族羧基官能化聚酯组分的合适的化合物A1是由含有5~13个碳原子的VERSATIC酸得到的化合物(VERSATIC是商标)。
可以理解的是,已经引入反应加合物组分A1中的两个高支化饱和羧酸(优选VERSATIC酸)可以相同或不同。
例如,酸VERSATIC10或VERSATIC9与CARDURA5可以以1∶1的摩尔比相互反应,或酸VERSATIC10可以与CARDURA5以1∶1的摩尔比反应或VERSATIC10酸与CARDURA10以1∶1的摩尔比反应以得到合适的组分A1。
可以理解的是,如果A1比例约为2,则由羧基官能化聚酯树脂和/或源于此的相应聚缩水甘油树脂组分得到的最终涂料组合物(其中A1的比例具有该值),显示出优异的颜料润湿性能和固化过程中涂层的流动性。
然而,也发现由羧基官能化聚酯树脂组分和/或聚缩水甘油树脂组分得到的粉末涂料(其中A1的比例明显小于2,希望为了达到最终固化涂料的特定Tg值),也显示出改进的颜料润湿和流动性。
为了获得源于上述特定线性聚酯和/或它们的相应线性聚缩水甘油酯的粉末涂料组合物的最佳性能,至少一种要引入组分A1中的VERSATIC酸必须具有相对小数目的碳原子(例如5个)。特别是VERSATIC5和VERSATIC10的结合是优选引入的。
在组分A1中,引入的两种支化酸更优选具有相对小数目的碳原子,且最优选仅使用酸VERSATIC5。
为了得到源于线性聚酯或上述聚缩水甘油酯的液体涂料组合物,使用由相对高分子量的VERSATIC酸、优选VERSATIC10酸得到的组分A1。
用于本发明方法的合适的化合物B是例如邻苯二甲酸(PA)、四氢化邻苯二甲酸、六氢化邻苯二甲酸(HHPA)、甲基六氢化邻苯二甲酸、桥亚甲基四氢化邻苯二甲酸、甲基桥亚甲基四氢化邻苯二甲酸、1,4-环己烷二羧酸和1,3-环己烷二羧酸或其混合物;其中HHPA是特别优选的。
用于本发明方法的合适的化合物C的典型例子是二羟甲基丙酸。
用于本发明方法中的合适的化合物D包括含有两个脂族羟基的支化脂族、脂环族或芳脂族化合物,其中每一羟基独立地或是伯羟基或是仲羟基,例如丙二醇、新戊二醇、氢化二羟苯基丙烷(HDPP)、氢化4,4′二羟基二苯基、1,4-环己烷二羟甲基、1,4-二羟基环己烷、羟基新戊酰羟基新戊酸酯和2-丁基-2-乙基-1,3-丙二醇或其混合物;其中HDPP是特别优选的。
如上所述按照本发明方法得到的线性叔脂族羧基官能化聚酯树脂,根据本领域公知方法能够容易地转变成聚缩水甘油酯树脂,该方法即在合适的碱和催化剂存在下与过量表卤醇反应。最合适的是使用表氯醇。
已经惊奇地发现本发明的线性叔脂族羧基官能化聚酯树脂和聚缩水甘油酯树脂都能够形成粉末涂料组合物,其显示明显改进的物理性能,且可根据组分A1、A2和A3之间的摩尔比并根据引入到组分A1中的每一VERSATIC残留物的类型而特制。例如如果组分A1中VERSATIC酸残留物存在明显差异(VERSATIC10和VERSATIC5酸)且其中A1/A2+A3摩尔比相对低(即HPA和/或HDPP量较大),则可得到作为最终产物的固体树脂。
对于优选的官能化聚酯和其缩水甘油酯,A2和A3的范围是0.1~1。
另一方面当存在主要量的由二酸(组分b)和二羟基单羧酸(组分c)形成的所谓软嵌段和较少量的二醇(组分a)和二酸(组分b)的混合物时,线性聚酯和源于此的相应聚缩水甘油酯能够用作涂料中的液体树脂。而且如果所有VERSATIC酸组分仅含有大数目的碳原子(例如VERSATIC10或VERSATIC9酸,其中VERSATIC10酸是优选的),则其液体性能更加明显。
可以理解的是,由于本发明聚缩水甘油酯树脂的聚合物性能,现在相对低量的毒性可以与优异的涂料性能结合起来。更具体地,已经实现了优异的耐候性和耐酸性与产生粘附和平滑外观的有吸引力的薄膜流动的结合。
发现了由本发明的线性叔脂族羧基官能化聚酯树脂得到的那些聚缩水甘油酯树脂,其A1范围是0.1~0.25,而X的范围是2~4,同时Y的范围是1~4,该聚缩水甘油酯树脂能够提供最优选的室外耐久性粉末涂料组合物。
另一方面发现了当Y的范围是0~2和/或A1含有C10或更高级的酸时,能够得到室温下的液体树脂。
本发明的可固化粉末涂料组合物可以通过下面方法制得:或是向上述本发明的线性叔脂族羧基官能化聚酯树脂中或是向通过将该线性叔脂族羧基官能化聚酯树脂缩水甘油化而制得的聚缩水甘油酯树脂中加入交联树脂。
用于本发明粉末涂料组合物中的交联化合物的量通常使交联化合物的反应性基团与线性叔脂族羧基官能化聚酯树脂中存在的叔脂族羧基或聚缩水甘油酯树脂中存在的环氧基团的量大致相等。
本发明的液体涂料组合物可以通过下面方法制得:或是向液体线性叔脂族羧基官能化聚酯树脂中或是向通过将该线性叔脂族羧基官能化聚酯树脂缩水甘油化而制得的液体聚缩水甘油酯树脂中加入液体交联树脂。
可以理解的是,该液体涂料组合物能够通过浸渍、喷涂或刷光或辊涂施加。
与本发明的线性叔脂族羧基官能化聚酯树脂一起使用的合适的交联树脂是例如室外耐久性环氧树脂,诸如本发明的聚缩水甘油酯树脂、欧洲专利申请公开EP518,408中公开的α、α′二支化二羧酸的二缩水甘油酯和欧洲专利申请公开EP366,205中公开的基于在每个α碳原子上带有两个烷基取代基的多羧酸的聚缩水甘油酯。
与本发明的聚缩水甘油酯树脂一起使用的合适的交联树脂是例如本发明的(相应)酸官能化聚酯树脂;固体多元酸例如癸二酸、1,12-十二烷双酸;酐例如聚壬二酸聚酐;酸官能化聚酯例如1mol三羟甲基丙烷和3mol六氢化邻苯二甲酸酐的反应产物,1,6-己二醇与摩尔过量的1,12-十二烷双酸的反应产物,4mol的1,10-癸烷二羧酸、1.49mol的己二醇、0.47mol的1,1,1三(羟甲基)丙烷和0.27mol季戊四醇的反应产物,4mol的1,10-癸烷二羧酸、1.2mol的己二醇、0.45mol的三羟甲基丙烷、0.29mol的季戊四醇和0.21mol的二羟甲基丙酸的反应产物和1mol六甲氧基甲基蜜胺和3mol羟基新戊酸的反应产物和胺型固化剂。
最优选的是线性叔脂族羧基官能化聚酯树脂和源于此的聚缩水甘油酯的混合物。
本发明的粉末涂料组合物可以进一步包含催化剂和视具体情况而存在的其它添加剂,如本领域公知的适用于粉末涂料组合物中的那些。
合适的催化剂是例如季铵和鏻盐;金属盐/化合物例如辛酸亚锡(Ⅱ);碱性化合物例如咪唑;和叔胺例如二氮杂双环/十一碳烯。
所用催化剂的量通常是基于粉末涂料组合物总重量的大约0.1~2wt%。
本发明的粉末涂料组合物的合适的固化时间和固化温度是在粉末涂料体系方面惯用的那些。
下面的实施例用来说明本发明,而不是将其范围限制到这些具体的实施方案中。实施例1
本发明的线性叔脂族羧基官能化聚酯1~4和两个用于比较的现有技术的聚酯(a和b)的制备。
按照表1中所示的摩尔量将化合物(a)~(f)加入到圆底玻璃反应器中,该反应器装有带有回流冷凝器的Dean & Stark分水器、温度控制器、氮气入口和搅拌器。
然后在30分钟内将混合物加热到150℃,并加入二甲苯(基于反应混合物总重量的5wt%)。在2小时内将反应混合物的温度升高到210℃,并保持在210℃直到达到上述的理论酸值为止。将由此形成的酸官能化聚酯出料并将其冷却到室温。
表1(*)
(*)给出的数字表示为了制备线性叔羧基官能化聚酯树脂1~4、a和b在实施例1的方法中加入到反应器中的特定化合物的摩尔量。
化合物 | 聚酯树脂 | 1 | 2 | 3 | 4 | 5 | a | b |
(a) | V-EPHV(A1) | 0.1 | 0.25 | 0.25 | 2 | 0.1 | - | - |
(b) | HPA(A2) | - | - | 1.75 | - | 1.9 | 2 | - |
(c) | HDPP(A3) | 1.9 | 1.75 | - | - | - | - | 2 |
(d) | HHPA | 5 | 7 | 9 | 7 | 5 | 9 | 8 |
(e) | DMPA | 3 | 4 | 2 | 6 | 3 | 2 | 4 |
(f) | HDPP | 1 | 2 | 6 | 0 | 1 | 6 | 3 |
由所用缩写表示的化合物是:V-EPHV: 由1mol的VERSATIC酸和1mol的VERSATIC酸的缩水甘油
酯(CARDURA)形成的反应产物HPA: 羟基新戊酸HHPA: 六氢化邻苯二甲酸酐DMPA: 二羟甲基丙酸HDPP: 氢化的二羟苯基丙烷
按照所论述的现有技术得到的官能化聚酯树脂的分子结构(a)和(b)是:a)HPA-(HHPA-DMPA)2-HHPA-(HDPP-HHPA)6-HPA
该反应产物是根据EP-A-0634434得到的树脂的样品。b)HDPP-(HHPA-DMPA)4-(HHPA-HDPP)4
该反应产物是根据EP-A-0720997得到的树脂的样品。实施例2
聚缩水甘油酯树脂Ⅰ~Ⅴ的制备。
将如实施例1中制备的其量相当于1羧基当量的线性叔脂族羧基官能化聚酯树脂1~4、a和b溶解于8mol表氯醇(ECH)和异丙醇(IPA)中。将溶液加入到装有温度控制器、搅拌器和回流冷凝器的3升玻璃反应器中。接着升温到70℃,然后在60分钟的时间内逐步加入1.2mol的NaOH水溶液。经过另外的10分钟反应时间后,将反应器内容物沉淀并使含水相与有机相分离。
将有机相真空闪蒸以除去水、IPA和ECH。
将得到的产物溶解于甲苯中并用水洗涤有机相三次,之后真空闪蒸有机相以除去甲苯。将由此得到的缩水甘油酯出料并冷却。制得的固体和液体聚缩水甘油酯树脂的性能列于表2中。
表2
(1)如实施例1中所制备。(2)用于比较的缩水甘油酯。(3)如实施例2中所制备。(4)通过使用Kofler Bench测定软化范围。
酸聚酯(1) | 1 | 2 | 3 | 4 | 5 | 比较的 | |
a(2) | b(2) | ||||||
酸值前体 | 1.60 | 1.78 | 1.16 | 2.52 | 3.18 | 1.28 | 1.20 |
缩水甘油酯Ⅰ~Ⅳ和A和B(3) | |||||||
Ⅰ | Ⅱ | Ⅲ | Ⅳ | A | B | ||
EGCmmol/kg | 1120 | 1330 | 950 | 1750 | 1000 | 980 | |
软化范围(4) | 85-90 | 70-80 | 85-90 | <50的半固体 | 90-95 | 90-95 |
本发明的粉末涂料组合物A和表示比较组合物的D和E。
表3中所示的所有成分在室温下混合,然后在Buss单螺杆挤出机上在110℃熔融共混。将挤出物冷却、压片、在精细磨机中研磨并经过106微米筛分选。将粉末静电喷涂在铬酸盐预处理过的2mm厚的铝板上。涂敷的板在200℃烘烤15分钟。最终的涂层(厚度为40-60微米)非常平滑、坚硬、有光泽并显示良好的机械性能和良好的耐候性。
表3
A | B | C | D | E | ||
缩水甘油酯 | Ⅰ | 583 | - | - | - | - |
(参见表2) | Ⅱ | - | 556 | - | - | - |
Ⅲ | - | - | 607 | - | - | |
A | - | - | - | 600 | - | |
B | - | - | - | - | 602 | |
聚酯5号 | 205 | 232 | 181 | 188 | 186 | |
二氧化钛 | 167 | 167 | 167 | 167 | 167 | |
Modaflow | 10.1 | 10.1 | 10.1 | 10.1 | 10.1 | 10.1 |
苯偶姻 | 6.8 | 6.8 | 6.8 | 6.8 | 6.8 | |
涂料性能涂料组合物 | A | B | C | Da | Eb | F=Ⅳ+聚酯5号 |
流出*视觉外观 | 4 | 5 | 4 | 3 | 2 | 5 |
加速耐候性** | 2300 | 2600 | 3500 | 3100 | 2200 | 3500 |
可以理解的是,D和E被认为是比较组合物且组合物C的性能应该与组合物D相比较,同时组合物A和B的性能与E的相比较。
*等级5=优异的外观;非常平滑和粘附。
3=中等至良好的外观;有一些桔皮皱纹。
1=非常差的粗糙外观。
**Atlas老化试验机中的小时,在光泽度下降50%之前进行SAE-J1960试验方法。
Claims (10)
1、由下面反应得到的线性、叔羧基官能化聚酯树脂a)至少一种化合物A1,包含下列组分的反应产物(ⅰ)下式的合成高支化饱和单羧酸异构体的混合物的缩水甘油酯:,其中R1、R2和R3是1~15个碳原子的烷基,这其中至少一个是甲基,每一种酸含有5~19、优选5~13个碳原子,和(ⅱ)该合成高支化饱和单羧酸的混合物,组分(ⅰ)和(ⅱ)的摩尔比为1∶1,该组分A1视具体情况而定与羟基新戊酸(A2)和/或氢化二羟苯基丙烷(A3)混合;b)至少一种包含两个芳族或仲脂族羧基的芳族或脂环族二羧酸化合物B或其酐;视具体情况而定c)至少一种包含一个叔脂族羧基和两个脂族羟基的二羟基单羧酸化合物C,其中每一羟基独立地是伯或仲羟基;和d)视具体情况而定至少一种包含两个脂族羟基的二醇化合物D,其中每一羟基独立地是伯或仲羟基;
化合物A1∶A2+A3∶B∶C∶D的摩尔比是A1∶(2-A1)∶X+Y+1∶X∶Y,其中A1的范围是0.1~2,Y的范围是0~6,X的范围是2~8,温度是100~225℃,直到基本上所有的在反应混合物中起始存在的非叔羧基已经反应为止。
2、权利要求1的线性、叔羧基官能化聚酯树脂,其中A1表示含有10个碳原子的高支化饱和单羧酸的缩水甘油酯和含有5个碳原子的高支化饱和单羧酸的反应产物。
3、权利要求1的线性、叔羧基官能化聚酯树脂,其中A1表示含有5个碳原子的高支化饱和单羧酸的缩水甘油酯和含有5个碳原子的高支化饱和单羧酸的反应产物。
4、权利要求1的线性、叔羧基官能化聚酯树脂,其中A1表示含有10个碳原子的高支化饱和单羧酸的缩水甘油酯和含有10个碳原子的高支化饱和单羧酸的反应产物。
5、一种通过在合适的碱存在下,使权利要求1~4中任一项的线性、叔羧基官能化聚酯树脂与表卤醇反应制得的聚缩水甘油酯树脂。
6、一种粉末涂料组合物,包含权利要求1~4中任一项的线性、叔脂族羧基官能化聚酯树脂和交联剂。
7、一种粉末涂料组合物,包含权利要求5的聚缩水甘油酯树脂和交联剂。
8、一种液体涂料组合物,包含权利要求1~4中任一项的线性叔脂族羧基官能化聚酯树脂和交联剂。
9、一种液体涂料组合物,包含权利要求5的聚缩水甘油酯树脂和交联剂。
10、用权利要求6和7的涂料组合物涂敷的制品。
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US (1) | US5869191A (zh) |
EP (1) | EP0939781A1 (zh) |
KR (1) | KR20000057167A (zh) |
CN (1) | CN1234043A (zh) |
AU (1) | AU715038B2 (zh) |
BR (1) | BR9713410A (zh) |
CA (1) | CA2271202A1 (zh) |
HU (1) | HUP0000400A3 (zh) |
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JP2001131270A (ja) * | 1999-11-04 | 2001-05-15 | Japan Epoxy Resin Kk | 酸官能性及びエポキシ官能性ポリエステル樹脂 |
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CN110927860A (zh) * | 2018-09-19 | 2020-03-27 | 普睿司曼股份公司 | 具有交联二次涂层的光纤 |
CN110927860B (zh) * | 2018-09-19 | 2023-03-31 | 普睿司曼股份公司 | 具有交联二次涂层的光纤 |
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HUP0000400A2 (hu) | 2000-08-28 |
CA2271202A1 (en) | 1998-06-04 |
BR9713410A (pt) | 2000-04-18 |
WO1998023661A1 (en) | 1998-06-04 |
AU715038B2 (en) | 2000-01-13 |
NZ334764A (en) | 2000-01-28 |
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