CN103408719B - A kind of soft solvent-proof polyurethane elastomer and preparation method thereof - Google Patents
A kind of soft solvent-proof polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN103408719B CN103408719B CN201310334150.1A CN201310334150A CN103408719B CN 103408719 B CN103408719 B CN 103408719B CN 201310334150 A CN201310334150 A CN 201310334150A CN 103408719 B CN103408719 B CN 103408719B
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Abstract
The invention discloses a kind of soft solvent-proof polyurethane elastomer and preparation method thereof, its raw material is made up of two portions, and component A comprises polyester polyol 100 parts, tolylene diisocyanate 15 ~ 30 parts, tenderizer 0 ~ 20 part, filler 3 ~ 10 parts; B component chainextender 100 parts, defoamer 0 ~ 0.5 part, catalyzer 0.02 ~ 0.05 part.Chainextender is made up of alcamines chainextender and three-functionality-degree alcohols chainextender, wherein alcamines chainextender is the mixture of tri-isopropanolamine (TIPA) and diethanolamine (DEA) or trolamine (TEA), and the mol ratio of mixing is 1: 0.5 ~ 1.5; Three-functionality-degree alcohols chainextender is glycerine (GLY), TriMethylolPropane(TMP) (TMP) or trimethylolethane (TME) etc.; The mol ratio of three-functionality-degree alcohols chainextender and hydramine mixed chain extender is 1: 0.25 ~ 1.5.This material has good mechanical property, good solvent resistance and machinability.Can be used for the print fields such as color coating.
Description
Technical field
The present invention relates to soft solvent-proof polyurethane elastomer and preparation method thereof, particularly there is the product that can be used for the print fields such as color coating of excellent mechanical performances and solvent resistance.
Background technology
It is substrate that colour-coating technology to refer on tandem mill with cold rolled strip, galvanized steel (electro-galvanizing and pot galvanize) etc., through surface preparation (skimming treatment), by the method for roller coat, coat one or more layers different colours liquid coating, obtain the process of color coating sheet material through overbaking and cooling.Colored steel is widely used in the industries such as building, decoration, household electrical appliances, automobile, boats and ships.Due in coating that color coating line uses containing multi-solvents, therefore its roller coating machine needs a kind of solvent resistant polyurethane rubber roll of soft, also will have higher mechanical property and suitable operating procedure simultaneously.The durometer level of most of color coating rubber roll is at shore 50 ~ 60A.
Low hardness polyurethane material in the market for color coating rubber roll is generally polyester/tolylene diisocyanate (TDI) system, can be divided into adipate polyester and the large class of succinic acid polyester two by polyester kind.Poly-adipate polyester/TDI system has good mechanical property, but obviously swelling at ketone, ester class and alcohols isopolarity, in pimelinketone, soak 24h, and weightening finish can more than 50%, product shortening in work-ing life.The trade mark of rich Thunder God department of France exploitation is TD636 product, its performed polymer component is TDI and adipate polyester system, chain extender component is TriMethylolPropane(TMP) (TMP) and tri-isopropanolamine (TIPA), Article Stiffness Determination is shore 58A, tensile strength is 31MPa, tear strength is 46kN/m, and elongation is 450%, and pimelinketone soaks 24h weightening finish 56%.The solvent resistance of poly-succinic polyester system is better than poly-adipate polyester, but mechanical property is lower.A kind of synthetic method of solvent-proof polyurethane elastomer is reported in CN101130597, shore 50A goods are obtained with TDI and Dimethoxyethyl phthalate (DMEP) again with succinic acid, ethylene glycol, Diethylene Glycol and glycerine synthesizing polyester, this product can be used for color coating rubber roll, its tensile strength is 8MPa, tear strength is 22kN/m, and pimelinketone soaks 48h weightening finish 46%.People's (developments of Polyurethane Elastomers with Succinic Acid Polyester Polyols such as Yang Ruguo, white Shao Min, Institutes Of Technology Of Taiyuan's journal, the 35th volume, the 3rd phase, 362 pages ~ 364 pages) report a kind of Polyurethane Elastomers with Succinic Acid Polyester Polyols, synthesize performed polymer with poly-succinic ethylene glycol/binaryglycol ester and TDI, chainextender is TMP, and elastomer hardness is shore 58A, tensile strength is 19MPa, tear strength is 23.9kN/m, and elongation is 262%, and pimelinketone soaks 48h weightening finish 19%.
Summary of the invention
The technical problem to be solved in the present invention is to provide one soft solvent-proof polyurethane elastomer material, and this material has good mechanical property, good solvent resistance and machinability.Can be used for the print fields such as color coating.
Second technical problem that the present invention will solve is to provide a kind of preparation method of soft solvent-proof polyurethane elastomer material.
Low hardness polyurethane elastic body material of the present invention, its raw material is made up of performed polymer component (component A) and chain extender component (B component) two portions, comprises by mass parts:
(1) component A
(2) B component
Chainextender 100
Defoamer 0 ~ 0.5
Catalyzer 0.02 ~ 0.05
A/B＝100/6～12
Described polyester polyol is the reaction product of small molecules di-carboxylic acid and small molecules dibasic alcohol.The di-carboxylic acid be applicable to can be one or more in hexanodioic acid, pentanedioic acid, succinic acid, terephthalic acid, m-phthalic acid etc.The dibasic alcohol be applicable to can be ethylene glycol, 1,2-PD, 1,3-PD, butyleneglycol, 3-methyl-pentanediol, one or more in Diethylene Glycol, glycerine, hexylene glycol, neopentyl glycol etc.Polyester polyol of the present invention is generally the polyester diol of number-average molecular weight 1000-3000, and preferred number average molecular weight is hexanodioic acid system polyester diol and the Succinic Acid Polyester Polyols polyester diol of 1000-2000.
Tenderizer is one or more blending in diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP) (DOP), Dimethoxyethyl phthalate (DMEP), butyl benzyl phthalate (BBP), diethylene glycol dibenzoate (DEG), dipropylene glycol dibenzoate (DPG) etc.Filler is the mineral filler that polyurethane system is conventional, such as calcium carbonate, talcum powder, titanium dioxide etc.
Chainextender is made up of alcamines chainextender and three-functionality-degree alcohols chainextender, wherein alcamines chainextender is the mixture of tri-isopropanolamine (TIPA) and diethanolamine (DEA) or trolamine (TEA), and the mol ratio of mixing is 1: 0.5 ~ 1.5; Three-functionality-degree alcohols chainextender can select glycerine (GLY), TriMethylolPropane(TMP) (TMP) or trimethylolethane (TME) etc., preferred TMP; The mol ratio of three-functionality-degree alcohols chainextender and hydramine mixed chain extender is 1: 0.25 ~ 1.5.
Defoamer can select silicone antifoam agent; Catalyzer can select organo-bismuth or organic tin compound and combination thereof, and wherein organo-bismuth compounds is selected from isocaprylic acid bismuth or bismuth carboxylate etc. and combination thereof.Organic tin compound be selected from stannous octoate, two sad two fourth tin, dibutyl tin dilaurate etc. one or more, preferred organo-bismuth compounds, more preferably isocaprylic acid bismuth or bismuth carboxylate and combination thereof.
Low hardness polyurethane elastic body material of the present invention, adopts two-step approach preparation:
(1) preparation of component A: by polyester polyol, tenderizer and filler, by being metered into, reactor stirs, mixing 0.5 ~ 1h, material temperature rises to 120 ~ 130 DEG C, dehydration 2 ~ 3h, be cooled to 75 ~ 95 DEG C and add TDI, keep this thermotonus 1.5 ~ 2.5h, deaeration, cooling discharge, sealing is preserved.For making fillers dispersed even, before the dehydration of polyester polyol, tenderizer and filler, carry out blending dispersion by colloidal mill.
(2) preparation of B component: by chainextender, catalyzer and defoamer by being metered into reactor, temperature controls at 50 ~ 70 DEG C, and stir, mix 1 ~ 2h discharging, sealing is preserved.
(3) elastomeric preparation: component A temperature 70 ~ 90 DEG C, B component temperature 30 ~ 50 DEG C, die temperature 110 ~ 130 DEG C, gel time 30 ~ 40min, demould time 1 ~ 1.5h, postcure temperature is 120 ~ 125 DEG C, curing time 16 ~ 24h.Material cast can adopt machine to pour into a mould or hand dropping.
The performance of resulting product is in table 1.
Table 1 product performance
| Hardness/Shao A | 55～60 |
| Tensile strength/MPa | 25～35 |
| Tear strength/N/mm | 35～50 |
| Elongation/% | 400～500 |
| Rebound degree % | 35～45 |
| Pimelinketone soaks 24h weight rate (%) | ＜30 |
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Polyester polyol LM2856 in example is adipate glycol/propylene glycol ester polyester polyol that Liming Research Institute of Chemical Industry Co., Ltd. produces, molecular weight 2000; Polyester polyol LM7510 is succinic acid ethylene glycol/binaryglycol ester that Liming Research Institute of Chemical Industry Co., Ltd. produces, molecular weight 1000; POL-2456 is the hexanodioic acid series polyester polyol of space field, Qingdao chemical industry, and molecular weight is 2000.Defoamer is the BYK-028 that German Bi Ke BYK chemical company produces.
Embodiment 1
Component A is synthesized: first by after 1000g polyester polyol LM2856 and the mixing of 30g talcum powder; add colloidal mill (mill minimal adjustment distance 0.01mm) and carry out secondary blending dispersion; then get 515g and add reactor; be heated to 125 DEG C; dehydrated under vacuum 2h; material temperature is down to 70 DEG C, adds 100gTDI, 95 DEG C, react 1.5h under nitrogen protection.
B component is synthesized: 92gGLY, 191gTIPA, 75gTEA, 0.07g bismuth carboxylate and 0.7g defoamer are added reactor and carry out stirring, mixing, and temperature controls at 50 DEG C of mixing 1h.
Elastomers: after A, B in mass ratio 100/9.2 mixing deaeration, pour into 130 DEG C of 2mm moulds, the 60min demoulding, 125 DEG C of postcure 20h, room temperature surveys performance after placing 7 days.Resulting materials performance is in table 2.Embodiment 2
Component A is synthesized: after first being mixed by 1000g polyester polyol LM7510,200gDEP and 60g calcium carbonate; add colloidal mill and carry out secondary blending dispersion; then get 630g and add reactor; be heated to 125 DEG C; dehydrated under vacuum 2h; material temperature is down to 70 DEG C, adds 150gTDI, 75 DEG C, react 2h under nitrogen protection.
B component is synthesized: 134gTMP, 19.1gTIPA, 23gTEA, 0.1g isocaprylic acid bismuth and 0.6g defoamer are added reactor and carry out stirring, mixing, temperature controls at 70 DEG C of mixing time 1h.
Elastomeric preparation: after A, B in mass ratio 100/6 mixing deaeration, pour into 110 DEG C of 2mm moulds, the 90min demoulding, 120 DEG C of postcure 20h, room temperature surveys performance after placing 7 days.Resulting materials performance is in table 2.
Comparative example 1
Component A is synthesized: add 500g polyester polyol POL-2456,100gDMEP and 100g talcum powder in the reactor; be heated to 100-110 DEG C, after dehydrated under vacuum 3h, material temperature be down to 70 DEG C; add 100gTDI, 80 DEG C, react 3h under nitrogen protection and make to react completely.
B component is synthesized: 134gTMP, 48gTIPA, 0.1g isocaprylic acid bismuth and 0.6g defoamer are added reactor and carry out stirring, mixing, and temperature controls at 70 DEG C of mixing 1h.
Elastomeric preparation: after A, B in mass ratio 100/7 mixing deaeration, pour into 100 DEG C of 2mm moulds, the 60min demoulding, 100 DEG C of postcure 20h, room temperature surveys performance after placing 7 days.Resulting materials performance is in table 2.
Table 2 material property contrasts
| Test event | Embodiment 1 | Embodiment 2 | Comparative example 1 |
| Hardness/Shao A | 60 | 55 | 56 |
| Gel time/min | 40 | 30 | 45 |
| Demould time/h | 1 | 1.5 | 3 |
| Tensile strength/MPa | 35 | 25 | 25 |
| Tear strength/N/mm | 50 | 35 | 38 |
| Elongation/% | 460 | 405 | 410 |
| Rebound degree/% | 45 | 35 | 30 |
| Pimelinketone soaks 24h weight rate/% | 30 | 14 | 60 |
Claims (10)
1. a low hardness polyurethane elastic body material, its raw material is made up of performed polymer component A and chainextender B component two portions, comprises by mass parts:
(1) component A
(2) B component
Chainextender 100
Defoamer 0 ~ 0.5
Catalyzer 0.02 ~ 0.05
A/B＝100/6～12
Wherein chainextender is made up of alcamines chainextender and three-functionality-degree alcohols chainextender, wherein alcamines chainextender is the mixture of tri-isopropanolamine (TIPA) and diethanolamine (DEA) or trolamine (TEA), and the mol ratio of mixing is 1: 0.5 ~ 1.5; Three-functionality-degree alcohols chainextender is selected from glycerine (GLY), TriMethylolPropane(TMP) (TMP) or trimethylolethane (TME); The mol ratio of three-functionality-degree alcohols chainextender and hydramine mixed chain extender is 1: 0.25 ~ 1.5.
2. low hardness polyurethane elastic body material according to claim 1, it is characterized in that polyester polyol is the reaction product of small molecules di-carboxylic acid and small molecules dibasic alcohol, di-carboxylic acid is one or more in hexanodioic acid, pentanedioic acid, succinic acid, terephthalic acid, m-phthalic acid, dibasic alcohol is ethylene glycol, 1,2-propylene glycol, 1, ammediol, butyleneglycol, 3-methyl-pentanediol, one or more in Diethylene Glycol, hexylene glycol, neopentyl glycol; Tenderizer is one or more blending in diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP) (DOP), Dimethoxyethyl phthalate (DMEP), butyl benzyl phthalate (BBP), diethylene glycol dibenzoate (DEG), dipropylene glycol dibenzoate (DPG).
3. low hardness polyurethane elastic body material according to claim 2, is characterized in that polyester polyol is hexanodioic acid system polyester diol or the Succinic Acid Polyester Polyols polyester diol of number-average molecular weight 1000-2000.
4. low hardness polyurethane elastic body material according to claim 2, is characterized in that silicone antifoam agent selected by defoamer; Catalyzer selects organo-bismuth or organic tin compound and combination thereof.
5. low hardness polyurethane elastic body material according to claim 4, is characterized in that organo-bismuth compounds is selected from bismuth carboxylate, organic tin compound be selected from stannous octoate, two sad two fourth tin, dibutyl tin dilaurate one or more.
6. low hardness polyurethane elastic body material according to claim 5, is characterized in that catalyzer refers to isocaprylic acid bismuth.
7., according to the low hardness polyurethane elastic body material one of claim 1 ~ 6 Suo Shu, it is characterized in that pouring into a mould rear resulting product has following performance:
8. a preparation method for the low hardness polyurethane elastic body material that one of claim 1 ~ 7 is described, adopts two-step approach preparation:
(1) preparation of component A: by polyester polyol, tenderizer and filler, by being metered into, reactor stirs, mixing 0.5 ~ 1h, material temperature rises to 120 ~ 130 DEG C, dehydration 2 ~ 3h, be cooled to 75 ~ 95 DEG C and add TDI, keep this thermotonus 1.5 ~ 2.5h, deaeration, cooling discharge, sealing is preserved;
(2) preparation of B component: by chainextender, catalyzer and defoamer by being metered into reactor, temperature controls at 50 ~ 70 DEG C, and stir, mix 1 ~ 2h discharging, sealing is preserved;
(3) elastomeric preparation: component A temperature 70 ~ 90 DEG C, B component temperature 30 ~ 50 DEG C, die temperature 110 ~ 130 DEG C, gel time 30 ~ 40min, demould time 1 ~ 1.5h, postcure temperature is 120 ~ 125 DEG C, curing time 16 ~ 24h.
9. the preparation method of low hardness polyurethane elastic body material according to claim 8, carries out blending dispersion by colloidal mill before it is characterized in that the dehydration of polyester polyol, tenderizer and filler.
10. the preparation method of low hardness polyurethane elastic body material according to claim 8, is characterized in that material cast adopts machine cast or hand dropping.
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| CN103694440B (en) * | 2013-12-14 | 2016-08-03 | 常熟市永利化工有限公司 | Low hardness polyurethane elastic body material |
| CN104231222B (en) * | 2014-09-19 | 2017-07-07 | 黎明化工研究设计院有限责任公司 | A kind of High-abrasion-resistpolyurethane polyurethane elastomer and preparation method thereof |
| CN106589292A (en) * | 2016-12-30 | 2017-04-26 | 山东诺威聚氨酯股份有限公司 | High-rigidity and slow-gelling polyurethane elastomer and preparation method thereof |
| CN106750133B (en) * | 2016-12-30 | 2019-08-16 | 山东一诺威聚氨酯股份有限公司 | Low hardness polyurethane rubber roller material and preparation method thereof |
| CN107384289A (en) * | 2017-07-20 | 2017-11-24 | 江门市东业实业有限公司 | A kind of high thermal polyurethane PUR and three layers of heat sealing adhesive tape |
| CN109912777A (en) * | 2017-12-13 | 2019-06-21 | 上海优迈材料科技有限公司 | A kind of tear-proof floor-cleaning machine water suction adhesive tape and preparation method thereof |
| CN109970946A (en) * | 2017-12-27 | 2019-07-05 | 上海优迈材料科技有限公司 | A kind of preparation method of environmental protection low hardness polyurethane elastic body |
| CN109929089B (en) * | 2019-02-22 | 2021-12-28 | 黎明化工研究设计院有限责任公司 | Low-hardness high-strength solvent-resistant polyurethane elastomer and preparation method and application thereof |
| CN116751355B (en) * | 2023-08-17 | 2023-11-03 | 成都上泰科技有限公司 | Organic silicon modified polyurethane high polymer for soft-coated aluminum-plastic film of power battery and preparation method thereof |
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| CN102532464A (en) * | 2012-03-12 | 2012-07-04 | 烟台美瑞化学材料有限公司 | Low permanent compression deformation thermoplastic polyurethane elastomer |
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