CN104031229A - Polyurethane modified resin for air vane and preparation methods of polyurethane modified resin - Google Patents

Polyurethane modified resin for air vane and preparation methods of polyurethane modified resin Download PDF

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Publication number
CN104031229A
CN104031229A CN201410268427.XA CN201410268427A CN104031229A CN 104031229 A CN104031229 A CN 104031229A CN 201410268427 A CN201410268427 A CN 201410268427A CN 104031229 A CN104031229 A CN 104031229A
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China
Prior art keywords
modified resin
polyurethane
add
air vane
hydroxyl
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Application number
CN201410268427.XA
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Chinese (zh)
Inventor
杨伟
严序明
钱永嘉
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CHANGZHOU HUAKE RESIN Co Ltd
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CHANGZHOU HUAKE RESIN Co Ltd
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Priority to CN201410268427.XA priority Critical patent/CN104031229A/en
Publication of CN104031229A publication Critical patent/CN104031229A/en
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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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to polyurethane modified resin for an air vane and preparation methods of the polyurethane modified resin. The polyurethane modified resin is obtained through the steps of enabling polyester resin, hydroxyl acrylate and isocyanate to react, and then, diluting by using an unsaturated monomer. One of the preparation methods comprises the following steps of adding a catalyst into polyester resin; then, sequentially adding hydroxyl acrylate and isocyanate; heating to 60-80 DEG C, and reacting for 2-4h until the viscosity is up to the expected value; and finally, diluting by using the unsaturated monomer. The modified resin disclosed by the invention is high in strength and toughness, large in temperature difference, remarkable in cold tolerance and strength retention rate in cold or relatively hot areas, low in price, convenient to use, very low in viscosity and suitable for a vacuum introduction process and has the bending strength of at least 135MPa and the flexural modulus of at least 3000MPa; in addition, the invention provides the plurality of preparation methods of the polyurethane modified resin, and all the preparation methods are precise in designing process condition and adding sequence and capable of ensuring the product structure and molecular weight distribution of a resin product.

Description

A kind of polyurethane-modified resin and preparation method thereof for air vane
Technical field
The present invention relates to a kind of modified unsaturated polyester resin, particularly a kind of polyurethane-modified resin and preparation method thereof.
Background technology
Along with the development in new forms of energy market, air vane market also constantly expands.In order to pursue higher generating efficiency, blade length is more and more longer, and this just causes the increase of production time, and the performance of resin is also had higher requirement.Traditional air vane comprises epoxy resin with resin, Vinylite and unsaturated polyester resin.Wherein epoxy resin has the highest performance, but the difficulty of use.Vinylite intensity is better but price is higher.Unsaturated polyester resin is easy to use, cheap, but intensity is lower, and toughness is poor, can only do the blade that size is less.Polyurethane-modified resin is due to the existence of ammonia ester bond, intensity and the toughness of traditional unsaturated polyester resin are improved, large in the temperature difference, cold or have significant winter hardiness, strength retention ratio compared with hot area, simultaneously cheap, easy to use, viscosity is very low, is applicable to vacuum introducing technology, has best production efficiency.
Summary of the invention
The object of the invention is: the deficiency that overcomes air vane resin in prior art, a kind of high strength and toughness are provided, large in the temperature difference, cold or have significant winter hardiness compared with hot area, strength retention ratio, simultaneously cheap, easy to use, viscosity is very low, is applicable to polyurethane-modified resin and preparation method thereof for air vane of vacuum introducing technology.
Realizing the solution of the present invention is: the polyurethane-modified resin of a kind of air vane is by obtaining through unsaturated monomer dilution after the acrylate of vibrin, hydroxyl, isocyanate reaction;
Described vibrin reacts gained by carboxylic acid with organic polyhydric alcohol, and described carboxylic acid is phthalic anhydride, m-phthalic acid, terephthalic acid, maleic acid, FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, trimellitic acid 1,2-anhydride, tetrahydrophthalic anhydride, one or more of HHPA; Described organic polyhydric alcohol comprises methyl propanediol, 1,4 butyleneglycols, propylene glycol, ethylene glycol, Diethylene Glycol, dipropylene glycol, polyoxyethylene glycol, one or more of polypropylene glycol, the mixture of the wherein mixture of the mixture of multiple for example m-phthalic acid, terephthalic acid, maleic acid or FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE, or FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, trimellitic acid 1,2-anhydride.
Above-mentioned air vane with urethane resin its solidify after flexural strength be at least 135MPa, bending elastic modulus is at least 3000MPa.
The polyurethane-modified resin of above-mentioned air vane, the add-on of the acrylate of described hydroxyl is the acrylate of vibrin, hydroxyl and the 2-20% of isocyanic ester total mass, preferably 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%.
The polyurethane-modified resin of above-mentioned air vane, described vibrin hydroxyl value is more than or equal to 20, number-average molecular weight is 500～10000, the consumption correspondence of the hydroxyl value of vibrin and isocyanic ester, the too low modified effect of hydroxyl value is poor, and molecular weight determines viscosity and the performance of final product, under this hydroxyl value and number-average molecular weight scope, polyurethane-modified best results, the most applicable air vane resin of the viscosity of product and performance.
The polyurethane-modified resin of above-mentioned air vane, described hydroxy acryl acid ester is Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, one or more of Rocryl 410, the mixture of the wherein mixture of multiple for example Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, or Propylene glycol monoacrylate, Rocryl 410.
The polyurethane-modified resin of above-mentioned air vane, described isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate, 1, hexamethylene-diisocyanate, one or more of isophorone diisocyanate, wherein multiple for example tolylene diisocyanate, diphenylmethanediisocyanate, 1, the mixture of the mixture of hexamethylene-diisocyanate or hexamethylene diisocyanate, isophorone diisocyanate.
The polyurethane-modified resin of above-mentioned air vane, unsaturated monomer described in it comprises vinylbenzene, methyl methacrylate, one or more of Vinyl toluene, the mixture of the wherein mixture of multiple for example vinylbenzene, methyl methacrylate, or vinylbenzene, methyl methacrylate, Vinyl toluene.
The preparation method of polyurethane-modified resin for above-mentioned air vane, comprise the steps: to adopt conventional polyester synthetic method, alcohol and acid are added in 2L reactor, progressively be warming up to 200-210 degree, dehydration retains a part of hydroxyl, make vibrin hydroxyl value be more than or equal to 20, number-average molecular weight 500-10000.In vibrin, add the catalyzer dibutyl tin laurate of 0.01% (weight ratio).Then add successively acrylate and the isocyanic ester of hydroxyl, be warming up to 60-80 DEG C of reaction 2-4 hour, tested viscosity is to expection, for example cone-plate viscosity 4.5-5.5 pool, finally comprise vinylbenzene with unsaturated monomer, methyl methacrylate, one or more dilutions of Vinyl toluene.
Another preparation method of polyurethane-modified resin for above-mentioned air vane, comprise the steps: first synthesizing polyester resin, in synthetic vibrin, add the dibutyl tin laurate of isocyanic ester and catalyzer 0.01% (weight ratio), be warming up to 60-80 DEG C of reaction 2-4 hour, form isocyanate-terminated prepolymer, then add the acrylate of hydroxyl, 60-80 DEG C of insulation reaction 2-4 hour, tested viscosity is to expection, for example moor to cone-plate viscosity 6-8, finally comprise vinylbenzene with unsaturated monomer, methyl methacrylate, one or more dilutions of Vinyl toluene.
Another preparation method of polyurethane-modified resin for above-mentioned air vane, comprise the steps: first synthesizing polyester resin, then the acrylate of isocyanic ester and hydroxyl is added in 2L reactor, add the dibutyl tin laurate of catalyzer 0.01% (weight ratio), be warming up to 80 DEG C of reaction 2-4 hour, form isocyanate polymer, then add synthetic vibrin 60-80 DEG C insulation reaction 2-4 hour, tested viscosity is to expection, moor to cone-plate viscosity 2-2.5, finally comprise vinylbenzene with unsaturated monomer, methyl methacrylate, one or more dilutions of Vinyl toluene.Now the molecular weight distribution of product is wider.
The present invention has positive effect: (1) modified resin high strength of the present invention and toughness, large in the temperature difference, cold or have significant winter hardiness, strength retention ratio compared with hot area, simultaneously cheap, easy to use, viscosity is very low, applicable vacuum introducing technology; (2) modified resin of the present invention solidify after flexural strength high, flexural strength is at least 135MPa, bending elastic modulus is at least 3000MPa; (3) the invention provides the preparation method of multiple modified resin of the present invention, the accurate design technology condition of various preparation methods and order of addition(of ingredients), ensured product structure and the molecular weight distribution of resin product.
Embodiment
(embodiment 1)
By 550 grams of propylene glycol, 450 grams of MALEIC ANHYDRIDE, 500 grams of phthalic anhydrides, add in 2L reactor, be heated to 200 DEG C and moor to cone-plate viscosity 4.8, hydroxyl value 35, number-average molecular weight 1500, add 0.15 gram of dibutyl tin laurate, insulation, at 80 DEG C, adds 55 grams of methacrylic hydroxyl ethyl esters, 180 grams of tolylene diisocyanates, react 3 hours, with 700 grams of vinylbenzene dilutions.Tested viscosity and gel time.Add promotor and solidifying agent to solidify sold resin, make pour mass, test.
(embodiment 2)
By 550 grams of propylene glycol, 450 grams of MALEIC ANHYDRIDE, 500 grams of phthalic anhydrides, add in 2L reactor, be heated to 205 DEG C and moor to cone-plate viscosity 5.1, hydroxyl value 37, number-average molecular weight 1800, add 0.15 gram of dibutyl tin laurate, insulation, at 80 DEG C, adds 55 grams of methacrylic hydroxyl ethyl esters, 180 grams of tolylene diisocyanates, react 4 hours, by the mixture diluted of 700 grams of vinylbenzene, methyl methacrylate.Tested viscosity and gel time.Add promotor and solidifying agent to solidify sold resin, make pour mass, test.
(embodiment 3)
By 450 grams of polyoxyethylene glycol, 350 grams of FUMARIC ACID TECH GRADE acid anhydrides, 600 grams of phthalic anhydrides, add in 2L reactor, be heated to 210 DEG C and moor to cone-plate viscosity 7, hydroxyl value 25, number-average molecular weight 2700, add 0.14 gram of dibutyl tin laurate, insulation, at 70 DEG C, adds 150 grams of diphenylmethanediisocyanates, react 2 hours, add 80 grams of Hydroxyethyl acrylates, 80 DEG C of insulation reaction 1 hour, with 500 grams of vinylbenzene and 500 grams of methyl methacrylates dilutions again.Tested viscosity and gel time.Add promotor and solidifying agent to solidify sold resin, make pour mass, test.
(embodiment 4)
By 450 grams of polyoxyethylene glycol, 350 grams of FUMARIC ACID TECH GRADE acid anhydrides, 600 grams of phthalic anhydrides, add in 2L reactor, be heated to 208 DEG C and moor to cone-plate viscosity 8, hydroxyl value 28, number-average molecular weight 2900, add 0.14 gram of dibutyl tin laurate, insulation, at 75 DEG C, adds 150 grams of diphenylmethanediisocyanates, react 2 hours, add 80 grams of Hydroxyethyl acrylates, 80 DEG C of insulation reaction 1.5 hours, with 500 grams of vinylbenzene and 500 grams of methyl methacrylates dilutions again.Tested viscosity and gel time.Add promotor and solidifying agent to solidify sold resin, make pour mass, test.
(embodiment 5)
By 350 grams of methyl propanediol, 520 gram 1,4 butyleneglycols, 350 grams of maleic acids, 330 grams of terephthalic acids, 250 grams of tetrahydrophthalic anhydride add in 2L reactor, be heated to 204 DEG C and moor to cone-plate viscosity 2, hydroxyl value 65, number-average molecular weight 1200, insulation is at 80 DEG C, add the performed polymer (by 85 grams of methacrylic hydroxyl ethyl esters, 177 grams of isophorone diisocyanates and 0.17 gram of dibutyl tin laurate react under 4 hours and obtain under 60 degree) of methacrylic hydroxyl ethyl ester and isophorone diisocyanate, react 3 hours, with 1200 grams of vinylbenzene dilutions.Tested viscosity and gel time.Add promotor and solidifying agent to solidify sold resin, make pour mass, test.
(embodiment 6)
By 350 grams of methyl propanediol, 520 gram 1,4 butyleneglycols, 350 grams of maleic acids, 330 grams of terephthalic acids, 250 grams of tetrahydrophthalic anhydride add in 2L reactor, be heated to 210 DEG C and moor to cone-plate viscosity 2.3, hydroxyl value 66, number-average molecular weight 1800, insulation is at 80 DEG C, add the performed polymer (by 85 grams of methacrylic hydroxyl ethyl esters, 177 grams of isophorone diisocyanates and 0.17 gram of dibutyl tin laurate react under 4 hours and obtain under 60 degree) of methacrylic hydroxyl ethyl ester and isophorone diisocyanate, react 3 hours, with 1200 grams of vinylbenzene dilutions.Tested viscosity and gel time.Add promotor and solidifying agent to solidify sold resin, make pour mass, test.
The pour mass of above-described embodiment is pressed to GB8237 standard testing, and result is as follows
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (8)

1. the polyurethane-modified resin of air vane, is characterized in that: be by obtaining through unsaturated monomer dilution after the acrylate of vibrin, hydroxyl, isocyanate reaction;
Described vibrin reacts gained by carboxylic acid with organic polyhydric alcohol, and described carboxylic acid is phthalic anhydride, m-phthalic acid, terephthalic acid, maleic acid, FUMARIC ACID TECH GRADE, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, trimellitic acid 1,2-anhydride, tetrahydrophthalic anhydride, one or more of HHPA; Described organic polyhydric alcohol comprises methyl propanediol, Isosorbide-5-Nitrae butyleneglycol, propylene glycol, ethylene glycol, Diethylene Glycol, dipropylene glycol, polyoxyethylene glycol, one or more of polypropylene glycol.
2. the polyurethane-modified resin of air vane according to claim 1, is characterized in that: the add-on of the acrylate of described hydroxyl is the acrylate of vibrin, hydroxyl and the 2-20% of isocyanic ester total mass.
3. the polyurethane-modified resin of air vane according to claim 1, is characterized in that: described vibrin hydroxyl value is more than or equal to 20, and number-average molecular weight is 500～10000.
4. the polyurethane-modified resin of air vane according to claim 1, is characterized in that: described hydroxy acryl acid ester is Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, one or more of Rocryl 410.
5. the polyurethane-modified resin of air vane according to claim 1, is characterized in that: described isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, one or more of isophorone diisocyanate.
6. the preparation method with polyurethane-modified resin according to the arbitrary described air vane of claim 1～5, comprise the steps: to add catalyzer in vibrin, then add successively acrylate and the isocyanic ester of hydroxyl, be warming up to 60-80 DEG C, reaction 2-4 hour, tested viscosity, to expection, is finally diluted with unsaturated monomer.
7. the preparation method with polyurethane-modified resin according to the arbitrary described air vane of claim 1～5, comprise the steps: to add isocyanic ester and catalyzer in vibrin, be warming up to 60-80 DEG C, reaction 2-4 hour, form isocyanate-terminated prepolymer, then add the acrylate of hydroxyl, at 60-80 DEG C of insulation reaction 2-4 hour, tested viscosity, to expection, is finally diluted with unsaturated monomer.
8. the preparation method with polyurethane-modified resin according to the arbitrary described air vane of claim 1～5, comprise the steps: the acrylate of isocyanic ester and hydroxyl to add in reactor, add catalyzer, be warming up to 80 DEG C, reaction 2-4 hour, forms isocyanate polymer, then add vibrin, at 60-80 DEG C of insulation reaction 2-4 hour, tested viscosity, to expection, is finally diluted with unsaturated monomer.
CN201410268427.XA 2014-06-16 2014-06-16 Polyurethane modified resin for air vane and preparation methods of polyurethane modified resin Pending CN104031229A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106279626A (en) * 2016-08-23 2017-01-04 无锡市永亿精密铸造有限公司 A kind of composite for ultrasonic cavitron
CN109734860A (en) * 2019-01-10 2019-05-10 四川东树新材料有限公司 A kind of urethane composition for vacuum introducing technology
EP4130083A1 (en) 2021-08-03 2023-02-08 Covestro Deutschland AG Polyol composition

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WO2010131471A1 (en) * 2009-05-13 2010-11-18 Jsr株式会社 Kit for electrical wire water-sealing material, electrical wire water-sealing material, water-sealing member, water-sealed electrical wire, and water-sealing method
CN102153915A (en) * 2011-04-14 2011-08-17 兰州理工大学 Method for preparing unsaturated polyester and polyurethane segmented copolymer solvent-free printing ink
CN102504174A (en) * 2011-12-19 2012-06-20 烟台德邦科技有限公司 Polyurethane acrylic acid ester and preparation method and application thereof
CN103396525A (en) * 2013-07-22 2013-11-20 南通天和树脂有限公司 Unsaturated polyester resin for high-impact-resistance car bumper
CN103665310A (en) * 2013-12-13 2014-03-26 湖南邦弗特新材料技术有限公司 Preparation method of temperature-resistant UV (ultraviolet) curing resin

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101218266A (en) * 2005-05-17 2008-07-09 亚什兰许可和知识产权有限公司 Polyester-urethane (meth) acrylate resins
WO2010131471A1 (en) * 2009-05-13 2010-11-18 Jsr株式会社 Kit for electrical wire water-sealing material, electrical wire water-sealing material, water-sealing member, water-sealed electrical wire, and water-sealing method
CN102153915A (en) * 2011-04-14 2011-08-17 兰州理工大学 Method for preparing unsaturated polyester and polyurethane segmented copolymer solvent-free printing ink
CN102504174A (en) * 2011-12-19 2012-06-20 烟台德邦科技有限公司 Polyurethane acrylic acid ester and preparation method and application thereof
CN103396525A (en) * 2013-07-22 2013-11-20 南通天和树脂有限公司 Unsaturated polyester resin for high-impact-resistance car bumper
CN103665310A (en) * 2013-12-13 2014-03-26 湖南邦弗特新材料技术有限公司 Preparation method of temperature-resistant UV (ultraviolet) curing resin

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106279626A (en) * 2016-08-23 2017-01-04 无锡市永亿精密铸造有限公司 A kind of composite for ultrasonic cavitron
CN109734860A (en) * 2019-01-10 2019-05-10 四川东树新材料有限公司 A kind of urethane composition for vacuum introducing technology
EP4130083A1 (en) 2021-08-03 2023-02-08 Covestro Deutschland AG Polyol composition

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Application publication date: 20140910