CN114989387A - 一种双组分聚氨酯-聚脲弹性体及其制备方法、应用 - Google Patents
一种双组分聚氨酯-聚脲弹性体及其制备方法、应用 Download PDFInfo
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- CN114989387A CN114989387A CN202110877034.9A CN202110877034A CN114989387A CN 114989387 A CN114989387 A CN 114989387A CN 202110877034 A CN202110877034 A CN 202110877034A CN 114989387 A CN114989387 A CN 114989387A
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- polyurea elastomer
- polyol
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- 239000004970 Chain extender Substances 0.000 claims abstract description 35
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 19
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 26
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
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- 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 2
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- GUXGIGOQOIDDHU-UHFFFAOYSA-N 1-[4-[2-(2-hydroxyethoxy)ethyl]phenyl]ethanol Chemical compound OCCOCCC1=CC=C(C=C1)C(C)O GUXGIGOQOIDDHU-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 description 1
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 description 1
- KMBMQZQZBOLJHN-UHFFFAOYSA-N 2-methyloxirane;oxolane Chemical compound CC1CO1.C1CCOC1 KMBMQZQZBOLJHN-UHFFFAOYSA-N 0.000 description 1
- HQQTZCPKNZVLFF-UHFFFAOYSA-N 4h-1,2-benzoxazin-3-one Chemical class C1=CC=C2ONC(=O)CC2=C1 HQQTZCPKNZVLFF-UHFFFAOYSA-N 0.000 description 1
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical class C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
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- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 description 1
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
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- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
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- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
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- C08G18/3814—Polyamines
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- 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
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- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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- C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
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- 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
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- C08G18/40—High-molecular-weight compounds
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- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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Abstract
本发明涉及高分子材料合成技术领域,所属IPC分类号为C08G77/458,尤其涉及一种双组分聚氨酯‑聚脲弹性体及其制备方法。双组分聚氨酯‑聚脲弹性体,包括A组分和B组分,A组分的原料包括,按重量份计,多元醇A 70‑150份、二苯基甲烷二异氰酸酯20‑50份;B组分的原料包括,按重量份计,胺类扩链剂1‑5份、改性胺类扩链剂3‑20份、多次元醇B 3‑20份。本发明制作A组分中苯酐聚酯多元醇,聚己内酯多元醇,聚四氢呋喃醚多元醇混合使用,保障A组分使用稳定性与生产工艺的合理性同时,能够在光伏PCT,双85,UV老化等性能方面有更突出的性能。
Description
技术领域
本发明涉及高分子材料合成技术领域,所属IPC分类号为C08G77/458,尤其涉及一种双组分聚氨酯-聚脲弹性体及其制备方法。
背景技术
聚氨酯-聚脲弹性体因其结构中既有胺基甲酸酯,又有脲基甲酸酯基团,使其在机械性能方面具有更加突出的性能,具有强度好,伸长率高,耐磨,耐化学品酸、碱、盐、柴油、汽油、煤油、海水等介质的侵蚀,防腐性能卓越,且热稳定性较好,可在-50~140℃的空气环境下长期使用。该类弹性体在风机风能叶尖保护,直升机螺旋桨保护等领域一直非常广泛,但其制作工艺一直为少数公司所占有,我国并未有相关企业在该领域做出突破。
将聚氨酯-聚脲体系进行互混,由于伯胺与醚羟基活性差异大反应不均匀,造成性能波动大,衰减快,且无法做出稳定性能的材料,本质上难以实现。单纯的使用聚氨酯弹性体或聚脲弹性体,也不能承受双85,光伏PCT测试等具有恶劣户外使用要求的环境。现有公开的文献,未见能够满足风能风机叶片叶尖保护的弹性体材料,国内也未有相关企业有类似产品销售。专利CN 107207688 A中提到,使用由多羟基化合物、丁二醇和异氰酸酯制备了用于风力涡轮机叶片的聚氨酯材料,但并未对产品的机械性能或配方体系进行阐述,因此制作相关领域的材料必然需要使用特殊的方法才能实现,聚氨酯-聚脲体系的合成与稳定生产则是一种技术突破。
发明内容
为了能够更好的理解本发明的技术内容,结合以下本发明的优选实施方法的详述。
为了解决上述技术问题,本发明的第一个方面提供了一种双组分聚氨酯-聚脲弹性体,包括A组分和B组分。
A组分的原料包括,按重量份计,多元醇A70-150份、二苯基甲烷二异氰酸酯20-50份。
优选的,A组分的原料包括,按重量份计,多元醇A80-120份、二苯基甲烷二异氰酸酯30-40份。
所述多元醇A的重均分子量为1000-5000。
所述多元醇A为聚酯多元醇和/或聚醚多元醇。
优选的,所述多元醇A为聚酯多元醇和聚醚多元醇。
所述聚酯多元醇和聚醚多元醇的重量比(20-60):(40-80);优选的,所述聚酯多元醇和聚醚多元醇的重量比(30-50):(50-70)。
所述聚酯多元醇包括饱和脂肪族聚酯多元醇、不饱和脂肪族聚酯多元醇、己内酯系聚酯多元醇、芳香族聚酯多元醇中的至少一种。
优选的,所述聚酯多元醇包括己内酯系聚酯多元醇,具体的,所述己内酯系聚酯多元醇为聚己内酯二醇。
优选的,所述聚己内酯二醇的重均分子量为1000-3000;优选的,所述聚己内酯二醇的重均分子量为2000。
所述聚醚多元醇选自聚氧化丙烯二醇、聚四氢呋喃醚、四氢呋喃-氧化丙烯共聚二醇中的至少一种。
优选的,所述聚醚多元醇为聚四氢呋喃醚。
进一步优选的,所述聚四氢呋喃醚的重均分子量为1000-3000;优选的,所述聚四氢呋喃醚的重均分子量为2000。
在本发明中选用特定的聚四氢呋喃醚和聚己内酯二醇相互协同作用能够更好控制制品的拉伸强度和断裂伸长率。
优选的,所述聚酯多元醇还包括苯酐系列聚酯多元醇。
所述苯酐系列聚酯多元醇与聚酯多元醇的重量比为1:(1-6);优选的,所述苯酐系列聚酯多元醇与聚酯多元醇的重量比为1:(2-4)。
所述苯酐系列聚酯多元醇的酸值(AN)为0.10-0.50mgKOH/g、羟值(OHV)为70-85mgKOH/g、120℃的黏度为1550-1700mPa.S。
优选的,所述苯酐系列聚酯多元醇的酸值(AN)为0.30mgKOH/g、羟值(OHV)为78mgKOH/g、120℃的黏度为1610mPa.S。
所述苯酐系列聚酯多元醇的治本原料包括,酸组分、醇组分。
所述酸组分、醇组分的重量比为(500-600):(400-550);优选的,所述酸组分、醇组分的重量比为(500-550):(450-480)。
所述酸组分为苯酐或具有类似结构的二元酸,比如说丁二酸酐、顺丁烯二酸酐、邻苯二甲酸酐、苯酐等;优选的,所述酸组分为邻苯二甲酸酐。
所述醇组分为二元醇和/或三元醇。
优选的,所述醇组分为二元醇和三元醇;所述二元醇和三元醇的重量比为(300-500):(40-100);优选的,所述二元醇和三元醇的重量比为(350-450):(50-80);进一步优选的,所述二元醇和三元醇的重量比为(390-410):(60-70)。
所述二元醇选自己二醇,乙二醇,二乙二醇,新戊二醇,丁二醇,大于6个碳的二元醇中的至少一种。
所述三元醇为三羟甲基丙烷,甘油、三羟甲基乙烷中的至少一种。
优选的,所述二元醇为新戊二醇与己二醇的组合;所述三元醇为三羟甲基丙烷。
所述新戊二醇与己二醇的重量比为(400-600):(450-650);优选的,所述新戊二醇与己二醇的重量比为(450-500):(500-550)。
为了增加苯酐系列聚酯多元醇的抗氧性,还可根据需要在制备苯酐系列聚酯多元醇的时候加入0.1-0.3wt%的抗氧剂,所述抗氧剂为本领域公知的抗氧剂,抗氧剂的种类对本发明的技术效果并不会产生影响,比如说抗氧剂1010、抗氧剂1035、抗氧剂1076等均可使用。
制备苯酐系列聚酯多元醇的时候加入0.01-0.05%的催化剂然后使用载体熔融缩聚法和真空熔融缩聚法制备得到。
催化剂为本领域公知的催化剂,比如说锑系催化剂(氧化二锑、醋酸锑、乙二醇锑等)、钛系催化剂(钛酸四异丙酯、二氧化钛、钛酸四丁酯等)等。
具体的,所述聚酯多元醇的制备方法为:将酸组分、醇组分
在回流反应容器中,加热升温并通入氮气,体系至170℃时开始出水,并逐步升温至230℃,保温0.3-0.8h后加入钛酸四丁酯0.18g继续反应1-1.5h后开始梯度抽真空,并维持回流塔顶温度最高90℃,直至真空度达到-0.095Mbar,在230℃附近不断抽真空,监控酸值与羟值,最终得到苯酐系列聚酯多元醇。
申请人发现,使用聚四氢呋喃醚和聚己内酯二醇虽然能够较好的平衡制品哦拉伸性能,但是制品的耐高温性能不太好,可能是因为四氢呋喃醚和聚己内酯二醇并不能够很好的相容,经过大量研发实验,申请人发现,在体系中加入特定的苯酐系列聚酯多元醇能够较好的增加体系的稳定性,使得制品够在双85上的性能方面有更突出的性能,可能是因为特定比例的苯酐系列聚酯多元醇、聚四氢呋喃醚、聚己内酯二醇能够很好的互溶,保证了A组分使用稳定性与生产工艺的合理性。
在使用过程中,可根据需要向A组分中加入0.2-0.5重量份的抗氧剂,抗氧剂为本领域公知的抗氧剂。
B组分的原料包括,按重量份计,胺类扩链剂1-5份、改性胺类扩链剂3-20份、多次元醇B 3-20份。
优选的,所述B组分的原料包括,按重量份计,胺类扩链剂3-4改性胺类扩链剂5-18份、多次元醇B 6-13份。
所述胺类扩链剂选自MOCA、MDEA、MCDEA、MDA、MOEA、Unilink4200、Unilink4100、DETDA、DMTDA、天冬聚脲树脂中的至少一种。
其中,改性胺类扩链剂为胺类扩链剂改性得到;具体的,所述改性胺类扩链剂由单环氧类改性剂与胺类扩链剂混合制备得到;制备胺类扩链剂中,单环氧类改性剂与胺类扩链剂的质量比为1:2。
所述单环氧类改性剂选自叔碳酸缩水甘油酯E-10P,丁基缩水甘油醚,长链烷烃缩水甘油醚、苄基缩水甘油醚、苯基缩水甘油醚、和邻甲苯基缩水甘油醚中的一种或多种。
所述多元醇B至少包括聚醚多元醇B。
所述聚醚多元醇B选自对苯二酚二羟乙基醚(HQEE)、4-羟乙基氧乙基-1-1羟乙基苯二醚(HQEE-L)、三官能团的聚醚多元醇中的至少一种。
所述三官能团的聚醚多元醇的重均分子量为1000-6000;所述三官能团的聚醚多元醇包括聚丙二醇或环氧丙烷与环氧乙烷的共聚或嵌段共聚产品。
优选的,所述三官能团的聚醚多元醇为EP 3600或PPG 330N。
在一些实施方式中,所述多元醇B还包括乙二醇、1,4-丁二醇、三羟甲基丙烷、甘油、蓖麻油、氢化蓖麻油、三羟基甲基乙烷(TME)中的至少一种。
在一些实施方式中,可以根据需要向B组分中加入2-5重量份的助剂。
所述助剂包括光稳定剂、UV吸收剂、抗氧剂、色浆。
其中,光稳定剂、UV吸收剂、抗氧剂、色浆为本领域公知的助剂,可以列举的光稳定剂UV-9、UV-328、UV-531等;可以列举的UV吸收剂有苯并噁嗪酮、苯并吡喃酮、苯并三唑等。
在一些实施方式中,所述B组分中包括0.5-1重量份的光稳定剂、0.5-1重量份的UV吸收剂、0.5-1重量份的UV抗氧剂、1-1.5重量份的色浆。
虽然特定的A组分赋予了制品较好的耐高温性能,但是制品的耐PCT性能一般,现有技术中聚氨酯-聚脲体系进行互混得到的制品不能够承受双85,光伏PCT测试等具有恶劣户外使用要求的环境,与现有技术相比,申请人经过大量研究发现,在B组分中使用单环氧类改性剂与胺类扩链剂混合制备得到的改性胺类扩链剂很好的克服了伯胺与醚羟基活性差异大导致性能波动的缺陷,现有技术中二苯基甲烷二异氰酸酯与胺类扩链剂配合只适合做高硬度,本发明中,使用特定的多元醇和的改性胺类扩链剂能够很好的缩小二元胺与多元醇之间的反应活性差异,增加反应体系的稳定性和均质性,并且能够有效的降低体系的硬度。
所述A组分与B组分中质量比为100:(10-30);优选的,所述A组分与B组分中质量比为100:(12-25)。
本发明的第二个方面提供了一种双组分聚氨酯-聚脲弹性体及其制备方法,包括以下步骤:
(1)在反应容器中多元醇A、抗氧剂,充分搅拌并加热至100-120℃,抽真空除水0.3-1h,然后降温至50-80℃,加入二苯基甲烷二异氰酸酯,在氮气保护下,70-90℃反应2-3h,得到A组分
(2)将改性胺类扩链剂、胺类扩链剂、胺类扩链剂、助剂充分混合均匀,在100-120℃抽真空除水0.3-1h,得到B组分;
(3)A组分与B组分采用浇注工艺制得聚氨酯-聚脲弹性体。
所述浇注工艺的制备步骤为:
将A组分加热至100℃后与B组分充分混合,在保证无气泡的情况下倒入100-120℃的模具中,达到凝胶点后合模,放入100-120℃环境中固化16-48h得到聚氨酯-聚脲弹性体。
本发明的第三个方面提供了一种双组分聚氨酯-聚脲弹性体的应用,所述双组分聚氨酯-聚脲弹性体用于户外恶劣环境的保护装置,比如说风能风机叶片叶尖,直升飞机螺旋桨等装置的保护。
户外恶劣环境指的是85℃、85%RH的环境、光伏PCT测试的环境。
本发明具有下述有益效果:
1.现有技术中由于伯胺与醚羟基活性差异大导致制品性能的稳定性差,在本发明中通过特定的A组分和B组分克服了这一缺陷,并且还克服了MDI与MOCA等胺类扩链剂配合只适合做高硬度(大于85A)的缺陷,使大分子聚醚体系能够作为弹性体扩链剂使用,且性能稳定;
2.在本发明中使用二苯基甲烷二异氰酸酯,不使用一级危化品TDI,对生产与环境保护非常有益;
3.为了使得A组分能够具有稳定的性能,在本发明中,申请人制备了特定的苯酐系列聚酯多元醇与聚四氢呋喃醚和聚己内酯二醇相互协同作用保障A组分使用稳定性与生产工艺的合理性同时,能够在光伏PCT,双85,UV老化等性能方面有更突出的性能;
4.本发明中使用单环氧类改性剂对胺类进行了改性,降低了现有技术中二元胺与多元醇之间的反应活性差异,增加反应体系的稳定性和均质性,使得体系的稳定性能更好;
5.在本发明中通过特定比例的胺类扩链剂、改性胺类扩链剂的控制,并控制特定比例的A、B有效的降低了胺类扩链剂配合只适合做高硬度制品的缺陷。
具体实施方式
以下给出本发明的具体实施例,但本发明不受实施例的限制;另外,如果没有特殊说明,本发明中的原料均可由市售得到。
实施例1:一种双组分聚氨酯-聚脲弹性体,包括A组分和B组分;所述A组分的原料包括,按重量份计,聚己内酯二醇40份、聚四氢呋喃醚50份、苯酐系列聚酯多元醇10份、抗氧剂0.3份、二苯基甲烷二异氰酸酯32份;
所述聚己内酯二醇的重均分子量为2000;所述苯酐系列聚酯多元醇的重均分子量为1200;所述聚四氢呋喃醚的重均分子量为2000;
所述苯酐系列聚酯多元醇的制备方法为:将124.64g新戊二醇、278.13g己二醇、65.42g三羟甲基丙烷,531.80g邻苯二甲酸酐,3g抗氧剂加入到2L四口瓶中,加热升温并通入氮气,体系至170℃时开始出水,并逐步升温至230℃,保温0.5h后加入钛酸四丁酯0.18g继续反应,1.2h后开始梯度抽真空,并维持回流塔顶温度最高90℃,直至真空度达到-0.095Mbar,在230℃附近不断抽真空;所述苯酐系列聚酯多元醇的值(AN)为0.30mgKOH/g、羟值(OHV)为78mgKOH/g、120℃的黏度为1610mPa.S;
B组分的原料包括,按重量份计,胺类扩链剂(Unilink 4200)3份、改性胺类扩链剂(改性MOCA)18份、聚醚多元醇B(EP 3600)6份、光稳定剂0.88份、UV吸收剂0.88份、抗氧剂0.74份、色浆1.22份;
所述改性MOCA由MOCA与叔碳酸缩水甘油酯E-10P按质量比2:1混合制备得到;
所述A组分与B组分的重量比为100:22.5;
所述双组分聚氨酯-聚脲弹性体的制备方法包括:
(1)将聚己内酯二醇、苯酐系列聚酯多元醇、聚四氢呋喃醚、抗氧剂加入反应釜中,加热至110℃,充分搅拌下抽真空除水0.5h,然后降温至70℃,加入二苯基甲烷二异氰酸酯,在氮气保护条件下,80℃反应2h,得到A组分;
(2)将改性MOCA、Unilink 4200、EP 3600、光稳定剂、UV吸收剂、抗氧剂、色浆充分混合均匀,110℃下抽真空除水0.5h,得到B组分;
(3)将A组分与B组分采用浇注工艺制得聚氨酯-聚脲弹性体。
使用本领域公知的方法测定得到A组分的NCO含量为4.6wt%,粘度为4400mPa.S(80℃)。
实施例2:一种双组分聚氨酯-聚脲弹性体,包括A组分和B组分;所述A组分的原料包括,按重量份计,聚己内酯二醇20份、聚四氢呋喃醚70份、苯酐系列聚酯多元醇10份、抗氧剂0.3份、二苯基甲烷二异氰酸酯35份;
所述聚己内酯二醇、苯酐系列聚酯多元醇、聚四氢呋喃醚、抗氧剂同实施例1;
B组分的原料包括,按重量份计,胺类扩链剂(天冬聚脲树脂LF-AP106)3份、改性胺类扩链剂(改性天冬聚脲树酯LF-AP105)5份、聚醚多元醇B(PPG-330N)6份、1,4-丁二醇6.2份、光稳定剂0.94份、UV吸收剂0.94份、抗氧剂0.78份、色浆1.32份;
所述改性天冬聚脲树酯LF-AP105由天冬聚脲树酯LF-AP105与叔碳酸缩水甘油酯E-10P按质量比2:1混合制备得到;
所述A组分与B组分的重量比为100:15.7;
所述双组分聚氨酯-聚脲弹性体的制备方法包括:
(1)将聚己内酯二醇、苯酐系列聚酯多元醇、聚四氢呋喃醚、抗氧剂加入反应釜中,加热至110℃,充分搅拌下抽真空除水0.5h,然后降温至70℃,加入二苯基甲烷二异氰酸酯,在氮气保护条件下,80℃反应2h,得到A组分;
(2)将改性天冬聚脲树酯LF-AP105、天冬聚脲树脂LF-AP106、PPG-330N、1,4-丁二醇、光稳定剂、UV吸收剂、抗氧剂、色浆充分混合均匀,110℃下抽真空除水0.5h,得到B组分;
(3)将A组分与B组分采用浇注工艺制得聚氨酯-聚脲弹性体。
使用本领域公知的方法测定得到A组分的NCO含量为5.22wt%,粘度为2500mPa.S(60℃)。
对比例:一种双组分聚氨酯-聚脲弹性体,包括A组分和B组分;所述A组分的原料包括,按重量份计,聚己内酯二醇50份、聚四氢呋喃醚50份、抗氧剂0.3份、二苯基甲烷二异氰酸酯28份;
所述聚己内酯二醇、聚四氢呋喃醚、抗氧剂同实施例2;
B组分的原料包括,按重量份计,MOCA 9份、Unilink 4200 5.3份、PPG 330N8份、光稳定剂0.94份、UV吸收剂0.94份、抗氧剂0.78份、色浆1.32份。
所述光稳定剂、UV吸收剂、抗氧剂、色浆同实施例2;
所述A组分与B组分的重量比为100:16.52;
所述双组分聚氨酯-聚脲弹性体的制备方法包括:
(1)将聚己内酯二醇、聚四氢呋喃醚、抗氧剂加入反应釜中,加热至110℃,充分搅拌下抽真空除水0.5h,然后降温至70℃,加入二苯基甲烷二异氰酸酯,在氮气保护条件下,80℃反应2h,得到A组分;
(2)将MOCA、Unilink 4200、PPG-330N、光稳定剂、UV吸收剂、抗氧剂、色浆充分混合均匀,110℃下抽真空除水0.5h,得到B组分;
(3)将A组分与B组分采用浇注工艺制得聚氨酯-聚脲弹性体。
使用本领域公知的方法测定得到A组分的NCO含量为3.9wt%,粘度为3800mPa.S(60℃)。
性能测试
样品为实施例1-2和对比例中的A组分和B组分制备得测试样品;
样品的制备方法为:将A组份加热至100℃然后与B组分充分混合,在确保无气泡的情况下倒入110℃的模具中,达到凝胶点后合模,放入110℃环境中固化48h,室温放置至7天得到样品。
按照本领域公知的测试方法测试样品的性能,测试结果如表1所示:
表1
由表1的测试结果可知:常规的A组分与在室温环境下强度变化差异较大,通过高温高压PCT(121℃,2大气压,饱和水蒸气)或双85测试发现机械性随时间衰减明显,而本发明中特定的A组分和B组分制备得到的弹性体能够具有良好的耐光伏PCT,双85,UV老化性能。
Claims (10)
1.一种双组分聚氨酯-聚脲弹性体,包括A组分和B组分,其特征在于,A组分的原料包括,按重量份计,多元醇A70-150份、二苯基甲烷二异氰酸酯20-50份;B组分的原料包括,按重量份计,胺类扩链剂1-5份、改性胺类扩链剂3-20份、多次元醇B 3-20份。
2.根据权利要求1所述的一种双组分聚氨酯-聚脲弹性体,其特征在于,所述多元醇A为聚酯多元醇和/或聚醚多元醇。
3.根据权利要求2所述的一种双组分聚氨酯-聚脲弹性体,其特征在于,所述聚酯多元醇包括饱和脂肪族聚酯多元醇、不饱和脂肪族聚酯多元醇、己内酯系聚酯多元醇、芳香族聚酯多元醇中的至少一种。
4.根据权利要求2所述的一种双组分聚氨酯-聚脲弹性体,其特征在于,所述聚醚多元醇选自聚氧化丙烯二醇、聚四氢呋喃醚、四氢呋喃-氧化丙烯共聚二醇中的至少一种。
5.根据权利要求1-4任一项所述的一种双组分聚氨酯-聚脲弹性体,其特征在于,所述组分的原料还包括0.2-0.5重量份的抗氧剂。
6.根据权利要求1所述的一种双组分聚氨酯-聚脲弹性体,其特征在于,所述胺类扩链剂选自MOCA、MDEA、MCDEA、MDA、MOEA、Unilink4200、Unilink4100、DETDA、DMTDA、天冬聚脲树脂中的至少一种。
7.根据权利要求6所述的一种双组分聚氨酯-聚脲弹性体,其特征在于,所述改性胺类扩链剂由单环氧类改性剂与胺类扩链剂混合制备得到。
8.根据权利要求1或7所述的一种双组分聚氨酯-聚脲弹性体,其特征在于,所述多元醇B至少包括聚醚多元醇B。
9.一种根据权利要求1-8任一项所述的一种双组分聚氨酯-聚脲弹性体的制备方法,其特征在于,包括以下步骤:
(1)在反应容器中多元醇A、抗氧剂,充分搅拌并加热至100-120℃,抽真空除水0.3-1h,然后降温至50-80℃,加入二苯基甲烷二异氰酸酯,在氮气保护下,70-90℃反应2-3h,得到A组分
(2)将改性胺类扩链剂、胺类扩链剂、胺类扩链剂、助剂充分混合均匀,在100-120℃抽真空除水0.3-1h,得到B组分;
(3)A组分与B组分采用浇注工艺制得聚氨酯-聚脲弹性体。
10.一种权利要求1-8任一项所述的双组分聚氨酯-聚脲弹性体用于户外恶劣环境的保护装置。
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