CN102816317A - Glass fiber reinforced plastics based on 2,3-butanediol, and preparation method thereof - Google Patents
Glass fiber reinforced plastics based on 2,3-butanediol, and preparation method thereof Download PDFInfo
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- CN102816317A CN102816317A CN2011101518550A CN201110151855A CN102816317A CN 102816317 A CN102816317 A CN 102816317A CN 2011101518550 A CN2011101518550 A CN 2011101518550A CN 201110151855 A CN201110151855 A CN 201110151855A CN 102816317 A CN102816317 A CN 102816317A
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- butyleneglycol
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Abstract
The invention belongs to the preparation field of glass fiber reinforced plastics, and discloses a glass fiber reinforced plastics based on 2,3-butanediol, and a preparation method thereof. The glass fiber reinforced plastics have the following repetitive structure unit defined as in the description, wherein R1 is selected from -CH(CH3)-CH(CH3)- and -(CH2)o-; R2 is selected from -(CH2)p- and ortho-position-substituted benzene; n is from 1 to 100; m is from 1 to 100; o is from 2 to 13; and p is from 0 to 11. The invention also discloses the preparation method of the glass fiber reinforced plastics based on 2,3-butanediol. Products obtained by the method have light weight, high strength, good corrosion-resistant performance, thermal performance and electrical performance, and have wide applications in aviation, rocket, spacecraft, high voltage, insulation, heat-insulation and corrosion-resistant containers, and other products required to lighten self-weight.
Description
Technical field
The invention belongs to the glass-reinforced plastic material preparation field, be specifically related to a kind of based on 2, glass reinforced plastic of 3-butyleneglycol and preparation method thereof.
Background technology
The biology that has vital movement on the earth all is made up of organism; Organism can produce hexose and pentose through bio-transformation; Wherein hexose (mainly being glucose) is easy to fermentation, and pentose is representative with the wood sugar, is an important source of potential of main carbohydrate product.Wood sugar and glucose all are 2 through the primary product of Klebsiella oxytoca fermentation, the 3-butyleneglycol, and in addition, other mikrobe can produce 2, the 3-butyleneglycol like genus bacillus, aeromonas hydrophila and several kinds of husky thunder bacterium.Thereby, 2, the preparation production process of 3-butyleneglycol and other Chemicals are very different, and have been completely free of the dependence to industrial chemicals such as oil, also can avoid oil at use and the final a large amount of CO of waste simultaneously
2Discharging, and a series of problem such as the Global warming that causes thus, sandstorm, arid, flood.Therefore, 2, the 3-butyleneglycol is the environment-friendly material that utilizes renewable resources to produce, and meets the green theme of our times Sustainable development.
Nearly decades, a lot of science and research worker carried out comprehensive and systematic research to its performance.2, the 3-butyleneglycol is the liquid chemical of colorless and odorless, has very high boiling point and low zero pour, is used as preparation divinyl and frostproofer widely.In addition, 2, the thermal capacitance of 3-butyleneglycol is 27200J/g, and is suitable with ethanol (29100J/g), methyl alcohol (22100J/g), thereby can be used as liquid fuel and fuel dope.2, the dehydration of 3-butyleneglycol obtains the industrial solvent butanone, and further dehydration generates 1,3-butadiene (elastomeric starting raw material also is the important monomer of polymer industry).The butanone hydrogenation obtains high-octane high quality flight fuel, and the diacetate that the catalytic dehydrogenation esterification obtains is a kind of foodstuff additive of high price.
But when it is used as polymerization single polymerization monomer; Though with its isomers 1, the 4-butyleneglycol is the same, has two hydroxyls; But these two hydroxyls are secondary hydroxyl; Reactive behavior is very low, in polycondensation process, is difficult to the esterified prod that obtains higher molecular weight, has practical value with the diprotic acid reaction.Pointing out among the U.S.Pat.No.4600768 that for dicarboxylicacid and 2 product of 3-butyleneglycol preparation was not also reported, mainly is owing to lack a kind of appropriate preparation method.U.S.Pat.No.2502686 utilizes phthalic acid and 2, and the 3-butyleneglycol has prepared the polyester of a kind of lower molecular weight (1000～3000), and this lower molecular weight makes them can not be used to prepare profiled part, for example film and thin slice.U.S.Pat.No.3714126 is with 2, and the 3-butyleneglycol still at most only has been added to 8% as the properties-correcting agent of PET.
Excellent properties such as glass reinforced plastic is because its light weight and hard, non-conductive, and physical strength is high, corrosion-resistant can replace steel to make machine parts and (Zhao Deren etc., superpolymer synthesis technique, Chemical Industry Press, 1997, P303 such as automobile, ship housing.), have wide application field and market outlook.The most frequently used glass reinforced plastic is to solidify through crosslinking copolymerizations such as unsaturated polyester and vinylbenzene to obtain at present, and wherein, unsaturated polyester is by unsaturated dibasic acid and divalent alcohol polycondensation; The most frequently used divalent alcohol is a terepthaloyl moietie, sometimes in order to reduce cross-linking density, uses Ucar 35, glycol ether, 1; 3-butyleneglycol instead of part terepthaloyl moietie (Pan Zuren, polymer chemistry, Chemical Industry Press; 2002, P204.)。And with 2, the unsaturated polyester of 3-butyleneglycol and unsaturated dibasic acid prepared in reaction is that raw material production glass reinforced plastic also is not reported.
Summary of the invention
The purpose of this invention is to provide a kind of based on 2; The glass reinforced plastic of 3-butyleneglycol; This glass reinforced plastic light weight, intensity height, corrosion resistance nature, thermal property, electrical property are good, need alleviate at aviation, rocket, outer space vehicle, high pressure, insulation, thermal insulation, corrosion-resistant container and other all to have very widely aspect goods of deadweight to use.
Another object of the present invention provides a kind of above-mentioned based on 2; The preparation method of the glass reinforced plastic of 3-butyleneglycol; This method is through selecting polyester catalyst efficiently for use; Effectively utilize 2, the 3-butyleneglycol has prepared the unsaturated polyester that can be used for producing fibre glass product manufacture, opens two key radical polymerization crosslinking curings then and obtains glass reinforced plastic.
Technical scheme of the present invention is following:
The invention provides a kind of based on 2, the glass reinforced plastic of 3-butyleneglycol, this glass reinforced plastic has following repeated structural unit:
R
1Be selected from
R
2Be selected from
n＝1～100，m＝1～100，o＝2～13，p＝0～11。
Described R1 and R2 can be identical also can be different.
It is a kind of above-mentioned based on 2 that the present invention also provides, the preparation method of the glass reinforced plastic of 3-butyleneglycol, and this method may further comprise the steps:
With monomer a, MALEIC ANHYDRIDE and monomer b, 2; The 3-butyleneglycol and first catalyzer join in the flask that whipping appts and condensing works are housed according to a certain percentage; Vacuumize, inflated with nitrogen removes the oxygen in the reaction unit; Guarantee that transesterify and/or esterification carry out under condition of nitrogen gas, be heated to reaction mixture melt fully/be dissolved into homogeneous system after, control reaction temperature is 170～230 ℃; Stirring, reacting under the condensing condition, reaching more than 92% of Theoretical Calculation amount until the by product of transesterify and esterification;
Add second catalyzer, under 240～280 ℃, be evacuated to less than 500Pa, stir 0.5～6h, stopped reaction obtains unsaturated polyester;
In the unsaturated polyester that obtains, add a certain amount of initiator, 60～160 ℃ of following radical polymerization 0.5～12h promptly get product glass reinforced plastic;
Wherein, monomer a is selected from aliphatic dibasic acid, binary aliphatic ester, Tetra hydro Phthalic anhydride or their mixture; Monomer b is an aliphatic dihydroxy alcohol; The mass ratio of monomer a and MALEIC ANHYDRIDE is 4: 1～0: 1; Monomer b and 2, the mass ratio of 3-butyleneglycol are 0: 1～1: 1; The total amount of monomer a and MALEIC ANHYDRIDE and monomer b and 2, the mass ratio of the total amount of 3-butyleneglycol are 1: 1～1: 3; First catalyzer, second catalyzer account for reactive component a, b, MALEIC ANHYDRIDE and 2, and the weight fraction of 3-butyleneglycol total amount is 0.001～0.5%, and preferred 0.005～0.3%; The weight fraction that initiator accounts for unsaturated polyester is 0.05～1%;
First catalyzer, second catalyzer are for transesterify and/or esterification being had the conventional catalyst of katalysis, based on the metallic compound of following element: Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La, Ce, Li and Ga.
Described aliphatic dibasic acid is selected from C
2～C
15Straight chain aliphatic dibasic acid or C
5～C
10The alicyclic diprotic acid of ring-type; Further preferred oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, 1; The mixture of one or more in 2-cyclohexane cyclohexanedimethanodibasic or the 1,4 cyclohexanedicarboxylic acid; More preferably hexanodioic acid.
Described binary aliphatic ester is selected from the C of aliphatic dibasic acid
1-C
6Alkyl ester; Preferred dimethyl adipate.
Described aliphatic dihydroxy alcohol is selected from C
2～C
13Alkanediol; Further preferred terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, 1,4-butyleneglycol, 1; 5-pentanediol, NSC 6366,1,6-pinakon, 1,7-heptanediol, 1,8-ethohexadiol, 1; 9-nonanediol, decamethylene-glycol, 1,11-undecane glycol, 1; 12-dodecanediol, 1,13-tridecane glycol or 2-methyl isophthalic acid, the mixture of one or more in the ammediol; More preferably 1,4-butyleneglycol or terepthaloyl moietie.
Described catalyst component first catalyzer is selected from one or both the mixture in titanium compound or the acetate.
Described catalyst component second catalyzer is selected from a kind of in titanium compound, tin compound or the antimony compounds or their any mixture.
First catalyzer, second catalyzer can be same substances in reaction, also can be different substancess.
Described titanium compound is selected from a kind of in tetra-n-butyl titanate, tetraethyl titanate, metatitanic acid four n-propyls, titanium isopropylate or the metatitanic acid four different monooctyl esters or their any mixture.
Described acetate is selected from a kind of in zinc acetate, magnesium acetate or the manganese acetate or their any mixture.
Described tin compound is selected from a kind of in dibutyltin oxide, dibutyl tin laurate, stannous octoate or the tin protochloride or their any mixture.
Described antimony compounds is selected from one or both the mixture in antimony acetate or the Antimony Trioxide: 99.5Min.
Described initiator is selected from a kind of in dilauroyl peroxide, BPO, t-butylperoxyl benzoate, di-t-butyl peroxide, Diisopropyl azodicarboxylate or the ABVN, preferred Diisopropyl azodicarboxylate or BPO.
Further, prepare in the process of unsaturated polyester and add stopper vacuumizing polycondensation.
Described stopper is selected from Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone or 2,5 di tert butyl hydroquinone, preferred Resorcinol.
Further, after preparing unsaturated polyester, add free yl polymerizating monomer, wherein free yl polymerizating monomer is a solvent, is again polymerization single polymerization monomer, with two keys in the unsaturated polyester carry out free-radical polymerized, completion crosslinking curing process.
Described free yl polymerizating monomer is selected from the just own ester of vinylbenzene, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, TEB 3K, Jia Jibingxisuanyizhi, n propyl methacrylate, n-BMA or methylacrylic acid, optimization styrene.
Through changing the proportioning of free yl polymerizating monomer and unsaturated polyester, can make the unsaturated polyester resin of many kinds.
The present invention compares with prior art, has following advantage and beneficial effect:
1, the present invention utilize that reproducible biomass resource produces 2, the 3-butyleneglycol is a feedstock production glass reinforced plastic, has broken away from the depending on unduly of Nonrenewable resources such as oil, helps the protection of global environment and the sustainable development of chemical industry.
2, the present invention is through selecting polycondensation catalyst efficiently for use; Overcome 2, the not high shortcoming of 3-butyleneglycol secondary hydroxyl reactive behavior obtains unsaturated polyester with the unsaturated dicarboxylic acid anhydride reaction; As the raw material of producing glass reinforced plastic; Improved 2 greatly, the practical value of 3-butyleneglycol has good market outlook.
3,2 of the present invention's use; The 3-butyleneglycol has two pendant methyl, has destroyed the regularity of polyester molecule chain, makes product be difficult to crystallization; Radical polymerization obtains the colourless transparent glass steel, and the use in some field seems particularly important to this performance for glass reinforced plastic.
4, the glass reinforced plastic of the present invention's preparation can be through regulating MALEIC ANHYDRIDE and other diprotic acid, 2; The component proportions of 3-butyleneglycol and other divalent alcohol, unsaturated polyester and free yl polymerizating monomer and used diprotic acid and divalent alcohol kind; Thereby obtain the diversified fibre glass product manufacture of performance, can satisfy the variety requirement of different field material.
5, the product of the present invention's preparation has very high hardness, good rigidity and thermotolerance, all has very widely at aspects such as boats and ships, bathtub, container such as cold water tank, corrugated panel, tank cars and uses.
Embodiment
Below in conjunction with embodiment the present invention is further described.
In the following embodiment that provides, adopt following detection method:
Weight-average molecular weight M
wIn Waters 600E series GPC system, measure, wherein chloroform is used for working curve as elutriant and polystyrene standard sample.
Density:
The analytical balance Sartorius AC 120S that employing is equipped with Sartoius Kit YDK 01 carries out the density measurement according to Mohr Westphal method.This balance is kept at room temperature, and each test is approximately being carried out under the 2g polymer samples.
Embodiment 1
With 2 of 98g MALEIC ANHYDRIDE, 200g, 3-butyleneglycol, 0.06g tetra-n-butyl titanate.Join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add,, vacuumize to flask assembling one cover condensing works, inflated with nitrogen three times; The oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee esterification; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, esterification stirs 5h at 200 ℃, in this process; Water is steamed from reaction mixture as sub product, reaches 92% (water theory calculates the molar weight that molar weight equals MALEIC ANHYDRIDE) of Theoretical Calculation amount until the amount of water.
0.05g zinc acetate joins in the reaction mixture as the catalyzer of polycondensation.Polyreaction vacuumizes under 250 ℃ temperature and stirs 2h, promptly gets unsaturated polyester and gathers maleic acid 2, the 3-butanediol ester.
The gained unsaturated polyester is through test, and its weight-average molecular weight is 2500.
What obtain in the above gathers maleic acid 2, adds the 0.2g Diisopropyl azodicarboxylate in the 3-butanediol ester, and stirring places 80 ℃ convection oven to react 2h, promptly gets the transparent glass fiber reinforced plastics product.
The gained fibre glass product manufacture is through test, and density is 1.2g/cm
3, flexural strength is 180MPa, thermal conductivity 1.32kJ/ (mhK).
Embodiment 2
With 2 of 49g MALEIC ANHYDRIDE, 73g hexanodioic acid, 150g, 1 of 3-butyleneglycol, 100g, 4-butyleneglycol, 0.93g magnesium acetate join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add; To flask assembling one cover condensing works; Vacuumize, inflated with nitrogen three times, the oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee esterification, be heated to reaction mixture melt fully/be dissolved into homogeneous system after; Esterification stirs 4h at 210 ℃; In this process, water is steamed from reaction mixture as sub product, reaches 92% (water theory calculates molar weight and 2 times of hexanodioic acid molar weight sums that molar weight equals 1 times of MALEIC ANHYDRIDE) of Theoretical Calculation amount until the amount of water.
0.93g Antimony Trioxide: 99.5Min joins in the reaction mixture as the catalyzer of polycondensation.Polyreaction vacuumizes under 260 ℃ temperature and stirs 1h, promptly gets unsaturated polyester and gathers maleic acid-co-hexanodioic acid 2,3-butyleneglycol-co-1,4-butyleneglycol copolyesters.
The gained unsaturated polyester is through test, and its weight-average molecular weight is 2900.
What obtain in the above gathers maleic acid-co-hexanodioic acid 2, and 3-butyleneglycol-co-1 adds the 0.8g BPO in the 4-butyleneglycol copolyesters, and stirring places 120 ℃ convection oven to react 1.5h, promptly gets the transparent glass fiber reinforced plastics product.
The gained fibre glass product manufacture is through test, and density is 1.1g/cm
3, flexural strength is 105MPa, thermal conductivity 1.14kJ/ (mhK).
Embodiment 3
With 2 of 30g MALEIC ANHYDRIDE, 59g Tetra hydro Phthalic anhydride, 52g dimethyl adipate, 150g, the terepthaloyl moietie of 3-butyleneglycol, 50g, 0.02g metatitanic acid four different monooctyl esters, 0.03g antimony acetate join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add; To flask assembling one cover condensing works, vacuumize, inflated with nitrogen three times, the oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee transesterify and esterification; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after; Transesterify and esterification stir 8h at 180 ℃, and in this process, water and methyl alcohol are steamed from reaction mixture as sub product; Reach 92% (water theory calculates molar weight and the Tetra hydro Phthalic anhydride molar weight sum that molar weight equals MALEIC ANHYDRIDE, and methyl alcohol Theoretical Calculation amount is 2 times of dimethyl adipate molar weights) of Theoretical Calculation amount until the amount of cut liquid.
0.02g magnesium acetate, 0.02g stannous octoate join in the reaction mixture as the catalyzer of polycondensation.Polyreaction vacuumizes under 240 ℃ temperature and stirs 3.5h, promptly gets unsaturated polyester and gathers maleic acid-co-phthalic acid-co-hexanodioic acid 2,3-butyleneglycol-co-terepthaloyl moietie copolyesters.
The gained unsaturated polyester is through test, and its weight-average molecular weight is 2800.
What obtain in the above gathers maleic acid-co-phthalic acid-co-hexanodioic acid 2, adds the 0.3g di-t-butyl peroxide in 3-butyleneglycol-co-terepthaloyl moietie copolyesters, and stirring places 150 ℃ convection oven to react 3h, promptly gets the transparent glass fiber reinforced plastics product.
The gained fibre glass product manufacture is through test, and density is 1.0g/cm
3, flexural strength is 84MPa, thermal conductivity 1.03kJ/ (mhK).
Embodiment 4
With 2 of 49g MALEIC ANHYDRIDE, 90g, 3-butyleneglycol, 0.03g titanium isopropylate.Join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add,, vacuumize to flask assembling one cover condensing works, inflated with nitrogen three times; The oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee esterification; Be heated to reaction mixture melt fully/be dissolved into homogeneous system after, esterification stirs 3h at 230 ℃, in this process; Water is steamed from reaction mixture as sub product, reaches 92% (water theory calculates the molar weight that molar weight equals MALEIC ANHYDRIDE) of Theoretical Calculation amount until the amount of water.
0.02g metatitanic acid four different monooctyl esters, 0.02g Resorcinol join in the reaction mixture.Polyreaction vacuumizes under 280 ℃ temperature and stirs 0.5h, promptly gets unsaturated polyester and gathers maleic acid 2, the 3-butanediol ester.
The gained unsaturated polyester is through test, and its weight-average molecular weight is 3500.
What obtain in the above gathers maleic acid 2, adds 52g vinylbenzene, 0.2g Diisopropyl azodicarboxylate in the 3-butanediol ester, and stirring places 80 ℃ convection oven to react 2h, promptly gets the transparent glass fiber reinforced plastics product.
The gained fibre glass product manufacture is through test, and density is 1.1g/cm
3, flexural strength is 123MPa, thermal conductivity 1.18kJ/ (mhK).
Embodiment 5
With 2 of 20g MALEIC ANHYDRIDE, 80g hexanodioic acid, 50g, the terepthaloyl moietie of 3-butyleneglycol, 50g, 0.002g titanium isopropylate join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add; To flask assembling one cover condensing works; Vacuumize, inflated with nitrogen three times, the oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee esterification, be heated to reaction mixture melt fully/be dissolved into homogeneous system after; Esterification stirs 10h at 170 ℃; In this process, water is steamed from reaction mixture as sub product, reaches 92% (water theory calculates molar weight and 2 times of hexanodioic acid molar weight sums that molar weight equals MALEIC ANHYDRIDE) of Theoretical Calculation amount until the amount of cut liquid.
0.002g dibutyl tin laurate joins in the reaction mixture as the catalyzer of polycondensation.Polyreaction vacuumizes under 240 ℃ temperature and stirs 6h, promptly gets unsaturated polyester and gathers maleic acid-co-hexanodioic acid 2,3-butyleneglycol-co-terepthaloyl moietie copolyesters.
What obtain in the above gathers maleic acid-co-hexanodioic acid 2, adds the 0.07g dilauroyl peroxide in 3-butyleneglycol-co-terepthaloyl moietie copolyesters, and stirring places 160 ℃ convection oven to react 0.5h, promptly gets the transparent glass fiber reinforced plastics product.
Embodiment 6
With 2 of 20g MALEIC ANHYDRIDE, 80g hexanodioic acid, 150g, the terepthaloyl moietie of 3-butyleneglycol, 150g, 2g zinc acetate join in the 250mL there-necked flask that mechanical stirring device is housed.After all material add; To flask assembling one cover condensing works; Vacuumize, inflated with nitrogen three times, the oxygen of removing in the reaction vessel carries out under condition of nitrogen gas to guarantee esterification, be heated to reaction mixture melt fully/be dissolved into homogeneous system after; Esterification stirs 2h at 230 ℃; In this process, water is steamed from reaction mixture as sub product, reaches 92% (water theory calculates molar weight and 2 times of hexanodioic acid molar weight sums that molar weight equals MALEIC ANHYDRIDE) of Theoretical Calculation amount until the amount of cut liquid.
The 2g tetra-n-butyl titanate joins in the reaction mixture as the catalyzer of polycondensation.Polyreaction vacuumizes under 280 ℃ temperature and stirs 0.5h, promptly gets unsaturated polyester and gathers maleic acid-co-hexanodioic acid 2,3-butyleneglycol-co-terepthaloyl moietie copolyesters.
What obtain in the above gathers maleic acid-co-hexanodioic acid 2, adds the 1.4g BPO in 3-butyleneglycol-co-terepthaloyl moietie copolyesters, and stirring places 60 ℃ convection oven to react 12h, promptly gets the transparent glass fiber reinforced plastics product.
Implementation process and detected result through each embodiment; But the knowledge capital invention preparation method utilizes 2 of renewable biomass resource production; The 3-butyleneglycol is a raw material, under the effect of effective catalyst, obtains can be used as the unsaturated polyester for preparing glass reinforced plastic with the unsaturated dibasic acid reaction.Through the kind and the ratio of regulating each reactive component, can obtain the different fibre glass product manufacture of performance, in fields such as boats and ships, furniture, tubing, bars very application prospects is arranged all.
Above-mentioned description to embodiment is can understand and use the present invention for the ease of the those of ordinary skill of this technical field.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. one kind based on 2, and the glass reinforced plastic of 3-butyleneglycol is characterized in that: this glass reinforced plastic has following repeated structural unit,
R
1Be selected from
R
2Be selected from
n＝1～100，m＝1～100，o＝2～13，p＝0～11。
2. claim 1 is described based on 2, and the preparation method of the glass reinforced plastic of 3-butyleneglycol is characterized in that: this method may further comprise the steps:
With monomer a, MALEIC ANHYDRIDE and monomer b, 2; The 3-butyleneglycol and first catalyzer join in the flask that whipping appts and condensing works are housed according to a certain percentage; Vacuumize, inflated with nitrogen removes the oxygen in the reaction unit; Guarantee that transesterify and/or esterification carry out under condition of nitrogen gas, be heated to reaction mixture melt fully/be dissolved into homogeneous system after, control reaction temperature is 170～230 ℃; Stirring, reacting under the condensing condition, reaching more than 92% of Theoretical Calculation amount until the by product of transesterify and esterification;
Add second catalyzer, under 240～280 ℃, be evacuated to less than 500Pa, stir 0.5～6h, stopped reaction obtains unsaturated polyester;
In the unsaturated polyester that obtains, add a certain amount of initiator, 60～160 ℃ of following radical polymerization 0.5～12h promptly get product glass reinforced plastic;
Wherein, monomer a is selected from aliphatic dibasic acid, binary aliphatic ester, Tetra hydro Phthalic anhydride or their mixture; Monomer b is an aliphatic dihydroxy alcohol; The mass ratio of monomer a and MALEIC ANHYDRIDE is 4: 1～0: 1; Monomer b and 2, the mass ratio of 3-butyleneglycol are 0: 1～1: 1; The total amount of monomer a and MALEIC ANHYDRIDE and monomer b and 2, the mass ratio of the total amount of 3-butyleneglycol are 1: 1～1: 3; First catalyzer, second catalyzer account for reactive component a, b, MALEIC ANHYDRIDE and 2, and the weight fraction of 3-butyleneglycol total amount is 0.001～0.5%, and preferred 0.005～0.3%; The weight fraction that initiator accounts for unsaturated polyester is 0.05～1%;
First catalyzer, second catalyzer are for transesterify and/or esterification being had the conventional catalyst of katalysis, based on the metallic compound of following element: Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La, Ce, Li or Ga.
3. according to claim 2 based on 2, the preparation method of the glass reinforced plastic of 3-butyleneglycol is characterized in that: described aliphatic dibasic acid is selected from C
2～C
15Straight chain aliphatic dibasic acid or C
5～C
10The alicyclic diprotic acid of ring-type; Further preferred oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, 1; The mixture of one or more in 2-cyclohexane cyclohexanedimethanodibasic or the 1,4 cyclohexanedicarboxylic acid; More preferably hexanodioic acid; Described binary aliphatic ester is selected from the C of aliphatic dibasic acid
1-C
6Alkyl ester; Preferred dimethyl adipate.
4. according to claim 2 based on 2, the preparation method of the glass reinforced plastic of 3-butyleneglycol is characterized in that: described aliphatic dihydroxy alcohol is selected from C
2～C
13Alkanediol; Further preferred terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, 1,4-butyleneglycol, 1; 5-pentanediol, NSC 6366,1,6-pinakon, 1,7-heptanediol, 1,8-ethohexadiol, 1; 9-nonanediol, decamethylene-glycol, 1,11-undecane glycol, 1; 12-dodecanediol, 1,13-tridecane glycol or 2-methyl isophthalic acid, the mixture of one or more in the ammediol; More preferably 1,4-butyleneglycol or terepthaloyl moietie.
5. according to claim 2 based on 2, the preparation method of the glass reinforced plastic of 3-butyleneglycol is characterized in that: described first catalyzer is selected from one or both the mixture in titanium compound or the acetate; Described second catalyzer is selected from a kind of in titanium compound, tin compound or the antimony compounds or their any mixture; Wherein, titanium compound is selected from a kind of in tetra-n-butyl titanate, tetraethyl titanate, metatitanic acid four n-propyls, titanium isopropylate or the metatitanic acid four different monooctyl esters or their any mixture; Acetate is selected from a kind of in zinc acetate, magnesium acetate or the manganese acetate or their any mixture; Tin compound is selected from a kind of in dibutyltin oxide, dibutyl tin laurate, stannous octoate or the tin protochloride or their any mixture; Antimony compounds is selected from one or both the mixture in antimony acetate or the Antimony Trioxide: 99.5Min.
6. according to claim 2 based on 2; The preparation method of the glass reinforced plastic of 3-butyleneglycol; It is characterized in that: described initiator is selected from a kind of in dilauroyl peroxide, BPO, t-butylperoxyl benzoate, di-t-butyl peroxide, Diisopropyl azodicarboxylate or the ABVN, preferred Diisopropyl azodicarboxylate or BPO.
7. according to claim 2 based on 2, the preparation method of the glass reinforced plastic of 3-butyleneglycol is characterized in that: further, prepare in the process of unsaturated polyester and add stopper vacuumizing polycondensation.
8. according to claim 7 based on 2; The preparation method of the glass reinforced plastic of 3-butyleneglycol; It is characterized in that: described stopper is selected from Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone or 2,5 di tert butyl hydroquinone, preferred Resorcinol.
9. according to claim 2 based on 2, the preparation method of the glass reinforced plastic of 3-butyleneglycol is characterized in that: further, after preparing unsaturated polyester, add free yl polymerizating monomer.
10. according to claim 9 based on 2; The preparation method of the glass reinforced plastic of 3-butyleneglycol; It is characterized in that: described free yl polymerizating monomer is selected from the just own ester of vinylbenzene, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, TEB 3K, Jia Jibingxisuanyizhi, n propyl methacrylate, n-BMA or methylacrylic acid, optimization styrene.
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| CN103497283A (en) * | 2013-09-30 | 2014-01-08 | 常州天马瑞盛复合材料有限公司 | Special thixotropic resin for manufacturing glass fiber reinforced plastic (FRP) vehicles and ship hulls, and preparation method thereof |
| CN103804660A (en) * | 2014-03-04 | 2014-05-21 | 中国科学院长春应用化学研究所 | Unsaturated aliphatic-polylactic acid segmented copolymer and preparation method thereof |
| CN105482087A (en) * | 2015-12-28 | 2016-04-13 | 肇庆福田化学工业有限公司 | Anti-yellowing unsaturated polyester resin and synthetic method thereof |
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| KR20090072518A (en) * | 2007-12-28 | 2009-07-02 | (주)디피아이 홀딩스 | Preparing method of unsaturated polyester resins containing phosphate and uv-curing flame retarding paint |
| CN101712751A (en) * | 2009-12-29 | 2010-05-26 | 岳阳昌德化工实业有限公司 | Method for synthesizing unsaturated polyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20090072518A (en) * | 2007-12-28 | 2009-07-02 | (주)디피아이 홀딩스 | Preparing method of unsaturated polyester resins containing phosphate and uv-curing flame retarding paint |
| CN101712751A (en) * | 2009-12-29 | 2010-05-26 | 岳阳昌德化工实业有限公司 | Method for synthesizing unsaturated polyester |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103497283A (en) * | 2013-09-30 | 2014-01-08 | 常州天马瑞盛复合材料有限公司 | Special thixotropic resin for manufacturing glass fiber reinforced plastic (FRP) vehicles and ship hulls, and preparation method thereof |
| CN103497283B (en) * | 2013-09-30 | 2016-06-29 | 常州天马瑞盛复合材料有限公司 | It is exclusively used in thixotroping resin of manufacture fiberglass vehicle and boats and ships housing and preparation method thereof |
| CN103804660A (en) * | 2014-03-04 | 2014-05-21 | 中国科学院长春应用化学研究所 | Unsaturated aliphatic-polylactic acid segmented copolymer and preparation method thereof |
| CN105482087A (en) * | 2015-12-28 | 2016-04-13 | 肇庆福田化学工业有限公司 | Anti-yellowing unsaturated polyester resin and synthetic method thereof |
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