CN102212242A - Method for preparing unsaturated polyester polyurethane block copolymer composite material - Google Patents
Method for preparing unsaturated polyester polyurethane block copolymer composite material Download PDFInfo
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Abstract
The invention discloses a method for preparing an unsaturated polyester polyurethane block copolymer composite material. The method comprises the following steps of: gradually polycondensing dihydric alcohol, maleic anhydride and phthalic anhydride to form a hydroxyl-terminated unsaturated polyester oligomer; gradually performing addition polymerization on the unsaturated oligomer, diisocyanate and polyethylene glycol by using styrene as a solvent to form solution of an isocyanate-terminated unsaturated polyester polyurethane block prepolymer; blocking the prepolymer by using hydroxyethyl acrylate to obtain an unsaturated polyester polyurethane block active prepolymer system containing double bonds; and compounding the active prepolymer system and glass fiber under the action of a redox initiator and a curing accelerator to obtain the unsaturated polyester polyurethane composite material.
Description
Technical field
The present invention relates to the preparation method of polymer composite.
Background technology
Unsaturated polyester resin (UPR) is the developing important kind of plastics industry in modern age, is being widely used aspect industry, agricultural, traffic, building and the national defense industry.UPR has excellent mechanical property, electrical property and resistance to chemical corrosion, and complete processing is easy, becomes in recent years one of the thermosetting resin comparatively rapidly of development both at home and abroad.Yet UPR is hard and crisp after solidifying, and impact property is poor, and therefore cure shrinkage height shortcomings such as (general cure shrinkage are 7%～8%), has limited its application to a certain extent.At present, the modification at UPR also mainly concentrates on its toughening modifying and low two aspects of modification of shrinking.
Fragility was big after UPR solidified, and shock strength is poor, is restricted in the practical application.In order to improve the shock resistance of UPR goods, often need UPR to carry out the toughness modification.From introducing the macromole flexible chain, the mobility that increases crosslinked network chain is considered, when synthesizing UPR, introduce soft segment, can effectively improve fragility, because the introducing of soft segment has increased the distance that UPR solidifies back two adjacent cross-linking set, increased the carbon-to-carbon singly-bound between the molecule crosslinked point, because of the ehter bond between cross-linking set flexible big, be easy to take place internal rotation, make change and segmental that segment between the resin reticulated structure cross-linking set under external force can occurred conformation stretch, show as kindliness preferably.Flexible diprotic acid commonly used and dibasic alcohol have polyester diol, glycol ether, two contract diffusing ethylene glycol, hexanodioic acid etc.But too much adding soft segment can cause that physical strength descends behind the resin solidification.
Is a kind of faster method of modifying of development in recent years based on the second phase material elastomerics to the UPR toughening modifying.What elastic body toughening was commonly used is that fluid rubber is toughness reinforcing, fluid rubber is homodisperse in UPR easily, rubber with active end group can be grafted on the UP main chain with the reaction of the UPR end group generation science of law, two alternate interface binding powers have been strengthened, improved consistency, system presents equal phase structure or submicroscopic phase separation structure.Owing to the high-flexibility of rubber phase, significantly improved the toughness of UP, though rubber elastomer can increase substantially shock strength, stretching, flexural strength, resistance toheat descend to some extent.
At present, the low contraction modification at UPR mainly is to reduce its cure shrinkage by adding thermoplasticity shrinking agent (LPA).Shrinking agent commonly used has polystyrene, polymethylmethacrylate and dially phthalate etc., has also developed polycaprolactone, modified polyurethane and cellulose acetate butyl ester etc.Adopt the fragility of LPA modification can improvement UPR, reduce cure shrinkage, improve shock strength, but can reduce the tensile strength of UPR.
Urethane has high-flexibility as the extraordinary elastomerics of a kind of property reconciled, and both maximize favourable factors and minimize unfavourable ones by bound energy, and performance advantage has separately not only reduced cure shrinkage, has also increased toughness.All the time, people concentrate on by adding polyurethane elastomer and UPR physical blending reaching the purpose of modification at the modification of UPR, but have often also reduced other mechanical property when improving its impelling strength, reduction cure shrinkage.
Summary of the invention
The preparation method who the purpose of this invention is to provide unsaturated polyester block polymers of polyurethane matrix material.
The present invention is the preparation method of unsaturated polyester block polymers of polyurethane matrix material, the steps include:
(1) terminal hydroxy group unsaturated polyester ester oligomer is synthetic: dibasic acid anhydride, ethylene glycol, dimethylbenzene, the vitriol oil that measures added successively be equipped with in electronic stirring, water trap, thermometer, the electric mantle heated reaction vessel, start stirring after being heated to the solid dissolving, and be warming up to 150 ℃, reaction 2h, be warming up to 190 ± 2 ℃ of reaction 1h, be cooled to 150 ℃ and add the ethylene glycol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, treat to add vinylbenzene when resin is cooled to below 50 ℃, stir, stop stirring, filter discharging, keep in Dark Place;
(2) preparation of unsaturated polyester block polymers of polyurethane: earlier with step 1 synthetic terminal hydroxy group unsaturated polyester ester oligomer UPR styrene solution, electronic stirring is equipped with in vulcabond and dibutyl tin laurate adding, condenser, thermometer, in the electric mantle heated reaction vessel, be warming up to 60 ℃ of insulation reaction, system system-NCO%, it is the isocyanate group content constant, add polyglycol ether carry out block reaction to-NCO% is constant, to polymerization system add the end-capping reagent measure carry out end capping to system-NCO% equals at 0 o'clock, stop heating, it is qualified to adjust viscosity with reactive thinner, stop stirring, filter discharging, keep in Dark Place;
(3) accurately mix in weighing unsaturated polyester block polymers of polyurethane styrene solution, initiator, curing catalyst and the container, after stirring, alkali free glass fibre is impregnated in the resin liquid that mixes, obtain unsaturated polyester block polymers of polyurethane matrix material through curing molding, and detect the every performance index of matrix material.
The present invention adopts dibasic alcohol, MALEIC ANHYDRIDE and phthalic anhydride to pass through progressively polycondensation and generates terminal hydroxy group unsaturated polyester ester oligomer; To be solvent with vinylbenzene generate the unsaturated polyester polyurethane blocks pre-polymer solution of isocyanate end through addition polymerization progressively for unsaturated oligopolymer and vulcabond, polyoxyethylene glycol; Prepolymer obtains terminal hydroxy group unsaturated polyester polyurethane blocks active prepolymer solution with the Hydroxyethyl acrylate end-blocking; The active prepolymer styrene solution under the redox initiator effect with the compound preparation unsaturated polyester of glass fibre compound polyurethane material.This matrix material has that cure shrinkage is low, breaking tenacity is high, impact resistance is good.
Embodiment
The present invention is the preparation method of unsaturated polyester block polymers of polyurethane matrix material, the steps include:
(1) the unsaturated polyester ester oligomer is synthetic
Dibasic acid anhydride, dibasic alcohol, solvent, the catalyzer that measures added successively be equipped with in electronic stirring, water trap, thermometer, the electric mantle heated reaction vessel, start stirring after being heated to the solid dissolving, and be warming up to 150 ℃, reaction 2h, be warming up to 190 ± 2 ℃ of reaction 1h, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, add stopper and stir, treat to add vinylbenzene when resin is cooled to below 50 ℃, stir, discharging is standby, keeps in Dark Place.
(2) the unsaturated polyester block polymers of polyurethane is synthetic
With the first step synthetic UPR styrene solution and the tolylene diisocyanate (TDI) and the polyglycol ether that measure, the adding of catalyzer dibutyl tin laurate is equipped with in electronic stirring, water trap, thermometer, the electric mantle heated reaction vessel, be warming up to 60 ℃ of insulation reaction, when-NCO%, be that isocyanate group content is when tending towards stability, add the methacrylic acid-β hydroxyl ethyl ester that measures, add little amount of catalyst dibutyl tin laurate and stopper again and continue reaction, to system-NCO% equals at 0 o'clock, stopped reaction, discharging is standby, keeps in Dark Place.
(3) preparation of unsaturated polyester block polymers of polyurethane matrix material
Accurate weighing unsaturated polyester block polymers of polyurethane styrene solution, initiator benzoyl peroxide, curing catalyst N, mix in accelerine and the container, after stirring, alkali free glass fibre is impregnated in the resin liquid that mixes, obtains unsaturated polyester block polymers of polyurethane matrix material through curing molding.
When the terminal hydroxy group unsaturated polyester ester oligomer of the above the first step was synthetic, it was saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, and MALEIC ANHYDRIDE is a unsaturated acid anhydride, and the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1.
When the terminal hydroxy group unsaturated polyester ester oligomer of the above the first step was synthetic, hydroxyl molar excess percentage ratio was 20%～100%, and the oligopolymer number-average molecular weight is 500～2000.
When the unsaturated polyester block polymers of polyurethane in the above second step prepared, hydroxy component was made up of terminal hydroxy group unsaturated polyester ester oligomer and polyoxyethylene glycol, and the two mol ratio is 1: 1～2; The polymerization degree of polyglycol ether is 5～10.
When the unsaturated polyester block polymers of polyurethane in the above second step prepared, vulcabond was a tolylene diisocyanate, and isocyanate group molar excess percentage ratio is 50%～100%, and the segmented copolymer number-average molecular weight is 2500～5000.
When the unsaturated polyester block polymers of polyurethane in the above second step prepared, end-capping reagent was methacrylic acid-β hydroxyl ethyl ester, and its consumption is 1.2～1.5 times of diisocyanate based molar excess number.
When the unsaturated polyester block polymers of polyurethane Composite Preparation in the above the 3rd step, the massfraction that multipolymer, solidifying agent, curing catalyst and alkali free glass fibre account for the matrix material total mass respectively is 65%～80%, 0.6%～1%, 8%～15%, 15%～30%.
When the unsaturated polyester block polymers of polyurethane Composite Preparation in the above the 3rd step, auxiliary agent comprises that initiator dibenzoyl peroxide, curing catalyst are N, accelerine.
Composite material solidification envrionment temperature of the present invention is not less than 20 ℃, 0.5 hour set time.
Further launch the present invention below in conjunction with specific embodiment:
(1) terminal hydroxy group unsaturated polyester ester oligomer is synthetic
With the 32.2g MALEIC ANHYDRIDE, the 231g Tetra hydro Phthalic anhydride, the 161g ethylene glycol and the 65g dimethylbenzene 2.6g vitriol oil add successively and are equipped with in electronic stirring, water trap, thermometer, the electric mantle heated reaction vessel, start stirring after being heated to the solid dissolving, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add 32.5g ethylene glycol, be evacuated to hydroxyl value and meet the requirements, steam dimethylbenzene, treat to add when resin is cooled to below 50 ℃ 130g vinylbenzene, stir, discharging is standby, keeps in Dark Place.
(2) the unsaturated polyester block polymers of polyurethane is synthetic
With 271g terminal hydroxy group unsaturated polyester ester oligomer styrene solution, 126.6g tolylene diisocyanate and 5.2g dibutyl tin laurate add in the there-necked flask that electronic stirring, condenser, thermometer, electric mantle heating are housed, be warming up to 60 ℃ of insulation reaction, to system-NCO%, it is the isocyanate group content constant, it is constant to system-NCO% that adding 112g polyglycol ether carries out block reaction, add 65g methacrylic acid-β hydroxyl ethyl ester react to system-NCO% equals at 0 o'clock, stopped reaction, discharging is standby, keeps in Dark Place.
(3) preparation of unsaturated polyester block polymers of polyurethane matrix material
Accurate weighing unsaturated polyester block polymers of polyurethane 100g, benzoyl peroxide 1g, N, accelerine 12g mixes in container, and then the 20g alkali free glass fibre be impregnated in mix in the resin liquid, can obtain unsaturated polyester block polymers of polyurethane matrix material behind the curing molding.Solidify drying back test material every performance index, test item and result such as table 1.
Table 1: unsaturated polyester block polymers of polyurethane composite property
Claims (9)
1. the preparation method of unsaturated polyester block polymers of polyurethane matrix material the steps include:
(1) terminal hydroxy group unsaturated polyester ester oligomer is synthetic: dibasic acid anhydride, ethylene glycol, dimethylbenzene, the vitriol oil that measures added successively be equipped with in electronic stirring, water trap, thermometer, the electric mantle heated reaction vessel, start stirring after being heated to the solid dissolving, and be warming up to 150 ℃, reaction 2h, be warming up to 190 ± 2 ℃ of reaction 1h, be cooled to 150 ℃ and add the ethylene glycol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, treat to add vinylbenzene when resin is cooled to below 50 ℃, stir, stop stirring, filter discharging, keep in Dark Place;
(2) preparation of unsaturated polyester block polymers of polyurethane: earlier with step 1 synthetic terminal hydroxy group unsaturated polyester ester oligomer UPR styrene solution, electronic stirring is equipped with in vulcabond and dibutyl tin laurate adding, condenser, thermometer, in the electric mantle heated reaction vessel, be warming up to 60 ℃ of insulation reaction, system system-NCO%, it is the isocyanate group content constant, add polyglycol ether carry out block reaction to-NCO% is constant, to polymerization system add the end-capping reagent measure carry out end capping to system-NCO% equals at 0 o'clock, stop heating, it is qualified to adjust viscosity with reactive thinner, stop stirring, filter discharging, keep in Dark Place;
(3) accurately mix in weighing unsaturated polyester block polymers of polyurethane styrene solution, initiator, curing catalyst and the container, after stirring, alkali free glass fibre is impregnated in the resin liquid that mixes, obtain unsaturated polyester block polymers of polyurethane matrix material through curing molding, and detect the every performance index of matrix material.
2. the preparation method of unsaturated polyester block polymers of polyurethane matrix material according to claim 1, it is characterized in that: when the terminal hydroxy group unsaturated polyester ester oligomer of the first step is synthetic, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is a unsaturated acid anhydride, and the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1.
3. the preparation of unsaturated polyester block polymers of polyurethane matrix material according to claim 1, it is characterized in that: when the terminal hydroxy group unsaturated polyester ester oligomer of the first step is synthetic, hydroxyl molar excess percentage ratio is 20%～100%, and the oligopolymer number-average molecular weight is 500～2000.
4. the preparation method of unsaturated polyester block polymers of polyurethane matrix material according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane in second step prepares, hydroxy component is made up of terminal hydroxy group unsaturated polyester ester oligomer and polyoxyethylene glycol, and the two mol ratio is 1: 1～2; The polymerization degree of polyglycol ether is 5～10.
5. the preparation method of unsaturated polyester block polymers of polyurethane matrix material according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane in second step prepares, vulcabond is a tolylene diisocyanate, isocyanate group molar excess percentage ratio is 50%～100%, and the segmented copolymer number-average molecular weight is 2500～5000.
6. the preparation method of unsaturated polyester block polymers of polyurethane matrix material according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane in second step prepares, end-capping reagent is methacrylic acid-β hydroxyl ethyl ester, and its consumption is 1.2～1.5 times of diisocyanate based molar excess number.
7. the preparation method of unsaturated polyester block polymers of polyurethane matrix material according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane Composite Preparation in the 3rd step, the massfraction that multipolymer, solidifying agent, curing catalyst and alkali free glass fibre account for the matrix material total mass respectively is 65%～80%, 0.6%～1%, 8%～15%, 15%～30%.
8. the preparation method of unsaturated polyester block polymers of polyurethane matrix material according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane Composite Preparation in the 3rd step, auxiliary agent comprises that initiator dibenzoyl peroxide, curing catalyst are N, accelerine.
9. the preparation method of unsaturated polyester block polymers of polyurethane matrix material according to claim 1 is characterized by the composite material solidification envrionment temperature and is not less than 20 ℃, 0.5 hour set time.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319727A (en) * | 2013-06-26 | 2013-09-25 | 兰州理工大学 | Unsaturated polyester polyurethane nano attapulgite material and preparation method thereof |
| CN103665311A (en) * | 2013-08-22 | 2014-03-26 | 常州大学 | Modified polyurethane/unsaturated polyester resin dibasic alcohol preparation method |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
| CN107522854A (en) * | 2017-09-27 | 2017-12-29 | 浙江天和树脂有限公司 | A kind of preparation method of high flexibility unsaturated polyester resin |
| CN107663264A (en) * | 2017-09-21 | 2018-02-06 | 广东溢达纺织有限公司 | A kind of unsaturated polyester resin without styrene and preparation method and application |
| CN111051377A (en) * | 2017-09-12 | 2020-04-21 | 科思创德国股份有限公司 | Composite material comprising a polyurethane-polyacrylate resin matrix |
| CN114702641A (en) * | 2022-04-20 | 2022-07-05 | 国网电力科学研究院武汉南瑞有限责任公司 | Modified polyurethane resin for electric power composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235129A (en) * | 2008-03-05 | 2008-08-06 | 安徽大学 | Method for preparing polybutadiene-base water polyurethane and modified emulsion thereof |
| CN101845118A (en) * | 2010-04-27 | 2010-09-29 | 广东天银化工实业有限公司 | Preparation method of hydroxy fluorine-containing water-based acrylic resin-polyurethane hybrid |
| JP2011057771A (en) * | 2009-09-08 | 2011-03-24 | Kawasaki Kasei Chem Ltd | Polyester polyol for polyurethane foam |
-
2011
- 2011-04-14 CN CN201110096329A patent/CN102212242B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235129A (en) * | 2008-03-05 | 2008-08-06 | 安徽大学 | Method for preparing polybutadiene-base water polyurethane and modified emulsion thereof |
| JP2011057771A (en) * | 2009-09-08 | 2011-03-24 | Kawasaki Kasei Chem Ltd | Polyester polyol for polyurethane foam |
| CN101845118A (en) * | 2010-04-27 | 2010-09-29 | 广东天银化工实业有限公司 | Preparation method of hydroxy fluorine-containing water-based acrylic resin-polyurethane hybrid |
Non-Patent Citations (1)
| Title |
|---|
| 《中国建材科技》 20110225 崔锦峰等 无溶剂常温固化不饱和聚酯聚氨酯涂料的研究 第38-42页 , 第01期 * |
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| CN103319727A (en) * | 2013-06-26 | 2013-09-25 | 兰州理工大学 | Unsaturated polyester polyurethane nano attapulgite material and preparation method thereof |
| CN103319727B (en) * | 2013-06-26 | 2015-05-13 | 兰州理工大学 | Unsaturated polyester polyurethane nano attapulgite material and preparation method thereof |
| CN103665311A (en) * | 2013-08-22 | 2014-03-26 | 常州大学 | Modified polyurethane/unsaturated polyester resin dibasic alcohol preparation method |
| CN103665311B (en) * | 2013-08-22 | 2016-04-13 | 常州大学 | A kind of dibasic alcohol preparation method of modified polyurethane/unsaturated polyester resin |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
| CN111051377A (en) * | 2017-09-12 | 2020-04-21 | 科思创德国股份有限公司 | Composite material comprising a polyurethane-polyacrylate resin matrix |
| CN111051377B (en) * | 2017-09-12 | 2022-05-13 | 科思创德国股份有限公司 | Composite material comprising a polyurethane-polyacrylate resin matrix |
| CN107663264A (en) * | 2017-09-21 | 2018-02-06 | 广东溢达纺织有限公司 | A kind of unsaturated polyester resin without styrene and preparation method and application |
| CN107663264B (en) * | 2017-09-21 | 2019-09-10 | 广东溢达纺织有限公司 | A kind of unsaturated polyester resin and the preparation method and application thereof without styrene |
| CN107522854A (en) * | 2017-09-27 | 2017-12-29 | 浙江天和树脂有限公司 | A kind of preparation method of high flexibility unsaturated polyester resin |
| CN114702641A (en) * | 2022-04-20 | 2022-07-05 | 国网电力科学研究院武汉南瑞有限责任公司 | Modified polyurethane resin for electric power composite material and preparation method and application thereof |
| CN114702641B (en) * | 2022-04-20 | 2024-07-02 | 国网电力科学研究院武汉南瑞有限责任公司 | Modified polyurethane resin for electric power composite material and preparation method and application thereof |
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