CN102816317B - 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
- Publication number
- CN102816317B CN102816317B CN201110151855.0A CN201110151855A CN102816317B CN 102816317 B CN102816317 B CN 102816317B CN 201110151855 A CN201110151855 A CN 201110151855A CN 102816317 B CN102816317 B CN 102816317B
- Authority
- CN
- China
- Prior art keywords
- butanediol
- reinforced plastic
- acid
- glass reinforced
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- CTQNGGLPUBDAKN-UHFFFAOYSA-N Cc1c(C)cccc1 Chemical compound Cc1c(C)cccc1 CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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 and R2 are selected from groups shown in the description; n= 1- 100; m= 1- to 100; o= 2-13; and p= 0- 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 glass-reinforced plastic material preparation field, be specifically related to a kind of glass reinforced plastic based on 2,3-butanediol and preparation method thereof.
Background technology
The biology earth with vital movement is all made up of organism, organism can produce hexose and pentose by bio-transformation, wherein hexose (mainly glucose) is easy to fermentation, and pentose is representative with wood sugar, is the potential important sources of of main sugar product.Xylose and glucose is all 2,3-butanediol through the primary product that Klebsiella oxytoca ferments, and in addition, other microorganism, as genus bacillus, aeromonas hydrophila and several husky thunder bacterium can produce 2,3-butanediol.Thus, preparation production process and other the Chemicals of 2,3-butanediol are very different, and have been completely free of the dependence to industrial chemicals such as oil, oil also can be avoided at use procedure and a large amount of CO of final waste simultaneously
2discharge, and a series of problem such as the Global warming caused thus, sandstorm, dry flood and drought damage.Therefore, 2,3-butanediol is the environment-friendly material utilizing renewable resources to produce, and meets the green theme of our times Sustainable development.
Nearly decades a lot of science and research worker comprehensive and systematic research has been carried out to its performance.2,3-butanediol is the liquid chemical of colorless and odorless, has very high boiling point and low zero pour, is widely used as and prepares divinyl and frostproofer.In addition, the thermal capacitance of 2,3-butanediol is 27200J/g, suitable with ethanol (29100J/g), methyl alcohol (22100J/g), thus can be used as liquid fuel and fuel dope.2,3-butanediol dehydration obtains industrial solvent butanone, and dehydration generates 1,3-butadiene (elastomeric starting raw material is also the important monomer of polymer industry) further.Butanone hydrogenation obtains high-octane high quality flight fuel, and the diacetate that catalytic dehydrogenation esterification obtains is a kind of foodstuff additive of high price.
But when it is used as polymerization single polymerization monomer, although with its isomers 1,4-butyleneglycol is the same, there are two hydroxyls, but these two hydroxyls are secondary hydroxyl, reactive behavior is very low, in polycondensation process, is difficult to be obtained by reacting higher molecular weight with diprotic acid, have the esterified prod of practical value.Point out in U.S.Pat.No.4600768 that the product prepared for dicarboxylic acid and 2,3-butanediol was not also reported, mainly owing to lacking a kind of suitable preparation method.The polyester of the U.S.Pat.No.2502686 a kind of lower molecular weight (1000 ~ 3000) that utilized phthalic acid and 2,3-butanediol to prepare, this lower molecular weight makes them can not be used to prepare profiled part, such as film and thin slice.U.S.Pat.No.3714126 using the properties-correcting agent of 2,3-butanediol as PET, but is only added to 8% at most.
The excellent properties such as glass reinforced plastic is hard, non-conductive due to its light weight, and physical strength is high, corrosion-resistant, can replace steel manufacturing machine part and (Zhao Deren etc., superpolymer synthesis technique, Chemical Industry Press, 1997, P303 such as automobile, ship housing.), have a wide range of applications field and market outlook.Glass reinforced plastic the most frequently used is at present obtained by the solidification of the crosslinking copolymerization such as unsaturated polyester and vinylbenzene, wherein, unsaturated polyester is by unsaturated dibasic acid and dibasic alcohol polycondensation, and the most frequently used dibasic alcohol is ethylene glycol, sometimes in order to reduce cross-linking density, propylene glycol, glycol ether, 1 can be used, 3-butyleneglycol replaces part ethylene glycol (Pan Zuren, polymer chemistry, Chemical Industry Press, 2002, P204.)。And react the unsaturated polyester prepared with 2,3-butanediol and unsaturated dibasic acid for raw material production glass reinforced plastic and yet there are no report.
Summary of the invention
The object of this invention is to provide a kind of based on 2, the glass reinforced plastic of 3-butyleneglycol, this glass reinforced plastic quality is light, intensity is high, corrosion resistance nature, thermal characteristics, electrical property are good, has and apply very widely in aviation, rocket, outer space vehicle, high pressure, insulation, thermal insulation, corrosion-resistant container and other goods needing to alleviate deadweight.
Another object of the present invention is to provide a kind of above-mentioned based on 2, the preparation method of the glass reinforced plastic of 3-butyleneglycol, the method is by selecting efficient polyester catalyst, effectively utilize 2,3-butyleneglycol has prepared the unsaturated polyester that can be used for producing fibre glass product manufacture, then opens double bond radical polymerization crosslinking curing and obtains glass reinforced plastic.
Technical scheme of the present invention is as follows:
The invention provides a kind of glass reinforced plastic based on 2,3-butanediol, 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 identical also can be different.
Present invention also offers a kind of preparation method of the above-mentioned glass reinforced plastic based on 2,3-butanediol, the method comprises the following steps:
By monomer a, MALEIC ANHYDRIDE and monomer b, 2,3-butyleneglycol and the first catalyzer join in the flask that whipping appts and condensing works are housed according to a certain percentage, vacuumize, inflated with nitrogen removing reaction unit in oxygen, ensure that transesterify and/or esterification are carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, controlling temperature of reaction is 170 ~ 230 DEG C, react, until the by product of transesterify and esterification reaches more than 92% of theoretical amount under stirring, condensing condition;
Add the second catalyzer, be evacuated to and be less than 500Pa at 240 ~ 280 DEG C, stir 0.5 ~ 6h, stopped reaction, obtains unsaturated polyester;
In the unsaturated polyester obtained, add a certain amount of initiator, radical polymerization 0.5 ~ 12h at 60 ~ 160 DEG C, obtains 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 aliphatic dihydroxy alcohol; The mass ratio of monomer a and MALEIC ANHYDRIDE is 4: 1 ~ 0: 1; The mass ratio of monomer b and 2,3-butanediol is 0: 1 ~ 1: 1; The mass ratio of the total amount of monomer a and MALEIC ANHYDRIDE and the total amount of monomer b and 2,3-butanediol is 1: 1 ~ 1: 3; First catalyzer, the second catalyzer account for reactive component a, b, the weight fraction of MALEIC ANHYDRIDE and 2,3-butanediol total amount is 0.001 ~ 0.5%, and preferably 0.005 ~ 0.3%; The weight fraction that initiator accounts for unsaturated polyester is 0.05 ~ 1%;
First catalyzer, the second catalyzer are conventional catalyst transesterify and/or esterification to katalysis, based on following element: the metallic compound of 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 diprotic acid or C
5~ C
10ring-type cycloaliphatic diacid; 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 further, the mixture of one or more in 2-cyclohexane cyclohexanedimethanodibasic or 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; Preferred ethylene glycol, 1,2-PD, 1,3-PD, 1 further, 4-butyleneglycol, 1,5-PD, neopentyl glycol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane, 1,12-dodecanediol, 1,13-tridecane diols or 2-methyl isophthalic acid, the mixture of one or more in ammediol; More preferably BDO or ethylene glycol.
Described catalyst component first catalyzer is selected from one or both the mixture in titanium compound or acetate.
Described catalyst component second catalyzer is selected from a kind of in titanium compound, tin compound or antimony compounds or their any mixture.
First catalyzer, the second catalyzer can be same substances in the 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-propyl, titanium isopropylate or the different monooctyl ester of metatitanic acid four or their any mixture.
Described acetate is selected from a kind of in zinc acetate, magnesium acetate or manganese acetate or their any mixture.
Described tin compound is selected from a kind of in dibutyltin oxide, dibutyl tin laurate, stannous octoate or tin protochloride or their any mixture.
Described antimony compounds is selected from one or both the mixture in antimony acetate or antimonous oxide.
Described initiator is selected from the one in dilauroyl peroxide, dibenzoyl peroxide, t-butylperoxyl benzoate, di-t-butyl peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile), preferred Diisopropyl azodicarboxylate or dibenzoyl peroxide.
Further, stopper is added vacuumizing polycondensation and prepare in the process of unsaturated polyester.
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 solvent, is again polymerization single polymerization monomer, carries out free-radical polymerized with the double bond in unsaturated polyester, completes crosslinking curing process.
Described free yl polymerizating monomer is selected from the just own ester of vinylbenzene, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, n-BMA or methacrylic acid, optimization styrene.
By changing the proportioning of free yl polymerizating monomer and unsaturated polyester, the unsaturated polyester resin of multi items can be obtained.
Compared with the existing technology, tool has the following advantages and beneficial effect in the present invention:
1, the present invention's 2,3-butanediol of utilizing reproducible biomass resource to produce prepares glass reinforced plastic for raw material, has broken away from depending on unduly Nonrenewable resources such as oil, has been conducive to the protection of global environment and the sustainable development of chemical industry.
2, the present invention is by selecting efficient polycondensation catalyst, overcome 2, the shortcoming that 3-butyleneglycol secondary hydroxyl reactive behavior is not high, unsaturated polyester is obtained by reacting with unsaturated dicarboxylic acid anhydride, as the raw material producing glass reinforced plastic, greatly improve the practical value of 2,3-butanediol, there are good market outlook.
3, the present invention use 2,3-butyleneglycol has two pendant methyl, destroys the regularity of polyester molecule chain, makes product be difficult to crystallization, radical polymerization obtains colourless transparent glass steel, and this performance seems particularly important for glass reinforced plastic in the use in some field.
4, the glass reinforced plastic prepared of the present invention is by regulating MALEIC ANHYDRIDE and other diprotic acid, 2, the component proportions of 3-butyleneglycol and other dibasic alcohol, unsaturated polyester and free yl polymerizating monomer and diprotic acid used and dibasic alcohol kind, thus obtain the diversified fibre glass product manufacture of performance, the diversity requirements of different field to material can be met.
5, the product that prepared by the present invention has very high hardness, well rigidity and thermotolerance, applies very widely as having in cold water tank, corrugated panel, tank car etc. at boats and ships, bathtub, container.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
In the following embodiment provided, adopt following detection method:
Weight-average molecular weight M
wwaters 600E series GPC system measures, and wherein chloroform is used for working curve as elutriant and polystyrene standard sample.
Density:
Adopt the density measurement that the analytical balance Sartorius AC 120S being equipped with Sartoius Kit YDK 01 carries out according to Mohr Westphal method.Maintained at room temperature by this balance, each test is carried out under about 2g polymer samples.
Embodiment 1
By the 2,3-butanediol of 98g MALEIC ANHYDRIDE, 200g, 0.06g tetra-n-butyl titanate.Join and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, a set of condensing works is assembled to flask, vacuumize, inflated with nitrogen three times, oxygen in removing reaction vessel is to ensure that esterification is carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, esterification stirs 5h at 200 DEG C, in the process, water is distilled out of from reaction mixture as byproduct, until the amount of water reaches 92% (water theory calculates the molar weight that molar weight equals MALEIC ANHYDRIDE) of theoretical amount.
0.05g zinc acetate joins in reaction mixture as the catalyzer of polycondensation.Polyreaction vacuumizes and stirs 2h at the temperature of 250 DEG C, obtains unsaturated polyester and gathers maleic acid 2,3-butanediol ester.
Gained unsaturated polyester is through test, and its weight-average molecular weight is 2500.
In poly-maleic acid 2,3-butanediol ester obtained above, add 0.2g Diisopropyl azodicarboxylate, the convection oven being placed in 80 DEG C that stirs reacts 2h, obtains transparent fibre glass product manufacture.
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
The BDO of the 2,3-butanediol of 49g MALEIC ANHYDRIDE, 73g hexanodioic acid, 150g, 100g, 0.93g magnesium acetate are joined and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, a set of condensing works is assembled to flask, vacuumize, inflated with nitrogen three times, oxygen in removing reaction vessel is to ensure that esterification is carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, esterification stirs 4h at 210 DEG C, in the process, water is distilled out of from reaction mixture as byproduct, until the amount of water reaches 92% (water theory calculates molar weight and the 2 times of hexanodioic acid molar weight sums that molar weight equals 1 times of MALEIC ANHYDRIDE) of theoretical amount.
0.93g antimonous oxide joins in reaction mixture as the catalyzer of polycondensation.Polyreaction vacuumizes and stirs 1h at the temperature of 260 DEG C, obtains unsaturated polyester and gathers maleic acid-co-hexanodioic acid 2,3-butanediol-co-1,4-butanediol copolyester.
Gained unsaturated polyester is through test, and its weight-average molecular weight is 2900.
At poly-maleic acid-co-hexanodioic acid 2,3-butanediol-co-1 obtained above, add 0.8g dibenzoyl peroxide in 4-butanediol copolyester, the convection oven being placed in 120 DEG C that stirs reacts 1.5h, obtains transparent fibre glass product manufacture.
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
The ethylene glycol of the 2,3-butanediol of 30g MALEIC ANHYDRIDE, 59g Tetra hydro Phthalic anhydride, 52g dimethyl adipate, 150g, 50g, the different monooctyl ester of 0.02g metatitanic acid four, 0.03g antimony acetate are joined and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, a set of condensing works is assembled to flask, vacuumize, inflated with nitrogen three times, oxygen in removing reaction vessel is to ensure that transesterify and esterification are carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, transesterify and esterification stir 8h at 180 DEG C, in the process, water and methyl alcohol are distilled out of from reaction mixture as byproduct, until the amount of cut liquid reach theoretical amount 92% (water theory calculates molar weight and equals molar weight and the Tetra hydro Phthalic anhydride molar weight sum of MALEIC ANHYDRIDE, methyl alcohol theoretical amount is 2 times of dimethyl adipate molar weights).
0.02g magnesium acetate, 0.02g stannous octoate join in reaction mixture as the catalyzer of polycondensation.Polyreaction vacuumizes and stirs 3.5h at the temperature of 240 DEG C, obtains unsaturated polyester and gathers maleic acid-co-phthalic acid-co-hexanodioic acid 2,3-butanediol-co-glycol copolyester.
Gained unsaturated polyester is through test, and its weight-average molecular weight is 2800.
In poly-maleic acid-co-phthalic acid-co-hexanodioic acid 2,3-butanediol-co-glycol copolyester obtained above, add 0.3g di-t-butyl peroxide, the convection oven being placed in 150 DEG C that stirs reacts 3h, obtains transparent fibre glass product manufacture.
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
By the 2,3-butanediol of 49g MALEIC ANHYDRIDE, 90g, 0.03g titanium isopropylate.Join and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, a set of condensing works is assembled to flask, vacuumize, inflated with nitrogen three times, oxygen in removing reaction vessel is to ensure that esterification is carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, esterification stirs 3h at 230 DEG C, in the process, water is distilled out of from reaction mixture as byproduct, until the amount of water reaches 92% (water theory calculates the molar weight that molar weight equals MALEIC ANHYDRIDE) of theoretical amount.
The different monooctyl ester of 0.02g metatitanic acid four, 0.02g Resorcinol join in reaction mixture.Polyreaction vacuumizes and stirs 0.5h at the temperature of 280 DEG C, obtains unsaturated polyester and gathers maleic acid 2,3-butanediol ester.
Gained unsaturated polyester is through test, and its weight-average molecular weight is 3500.
In poly-maleic acid 2,3-butanediol ester obtained above, add 52g vinylbenzene, 0.2g Diisopropyl azodicarboxylate, the convection oven being placed in 80 DEG C that stirs reacts 2h, obtains transparent fibre glass product manufacture.
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
The ethylene glycol of the 2,3-butanediol of 20g MALEIC ANHYDRIDE, 80g hexanodioic acid, 50g, 50g, 0.002g titanium isopropylate are joined and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, a set of condensing works is assembled to flask, vacuumize, inflated with nitrogen three times, oxygen in removing reaction vessel is to ensure that esterification is carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, esterification stirs 10h at 170 DEG C, in the process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (water theory calculates molar weight and the 2 times of hexanodioic acid molar weight sums that molar weight equals MALEIC ANHYDRIDE) of theoretical amount.
0.002g dibutyl tin laurate joins in reaction mixture as the catalyzer of polycondensation.Polyreaction vacuumizes and stirs 6h at the temperature of 240 DEG C, obtains unsaturated polyester and gathers maleic acid-co-hexanodioic acid 2,3-butanediol-co-glycol copolyester.
In poly-maleic acid-co-hexanodioic acid 2,3-butanediol-co-glycol copolyester obtained above, add 0.07g dilauroyl peroxide, the convection oven being placed in 160 DEG C that stirs reacts 0.5h, obtains transparent fibre glass product manufacture.
Embodiment 6
The ethylene glycol of the 2,3-butanediol of 20g MALEIC ANHYDRIDE, 80g hexanodioic acid, 150g, 150g, 2g zinc acetate are joined and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, a set of condensing works is assembled to flask, vacuumize, inflated with nitrogen three times, oxygen in removing reaction vessel is to ensure that esterification is carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, esterification stirs 2h at 230 DEG C, in the process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (water theory calculates molar weight and the 2 times of hexanodioic acid molar weight sums that molar weight equals MALEIC ANHYDRIDE) of theoretical amount.
2g tetra-n-butyl titanate joins in reaction mixture as the catalyzer of polycondensation.Polyreaction vacuumizes and stirs 0.5h at the temperature of 280 DEG C, obtains unsaturated polyester and gathers maleic acid-co-hexanodioic acid 2,3-butanediol-co-glycol copolyester.
In poly-maleic acid-co-hexanodioic acid 2,3-butanediol-co-glycol copolyester obtained above, add 1.4g dibenzoyl peroxide, the convection oven being placed in 60 DEG C that stirs reacts 12h, obtains transparent fibre glass product manufacture.
By implementation process and the detected result of each embodiment, known preparation method of the present invention utilize renewable biomass resource to produce 2,3-butyleneglycol is raw material, under the effect of effective catalyst, is obtained by reacting with unsaturated dibasic acid the unsaturated polyester that can be used as preparing glass reinforced plastic.By regulating kind and the ratio of each reactive component, the fibre glass product manufacture of different properties can be obtained, having application prospect very widely in fields such as boats and ships, furniture, tubing, bars.
The above-mentioned description to embodiment can understand and apply the invention for the ease of those skilled in the art.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (18)
1. based on a glass reinforced plastic for 2,3-butanediol, it is characterized in that: this glass reinforced plastic has following repeated structural unit,
R
1be selected from
R
2be selected from
or
n＝1～100，m＝1～100，p＝0～11；
The preparation method of the described glass reinforced plastic based on 2,3-butanediol, is characterized in that: the method comprises the following steps:
By monomer a, MALEIC ANHYDRIDE and monomer b, 2,3-butyleneglycol and the first catalyzer join in the flask that whipping appts and condensing works are housed according to a certain percentage, vacuumize, inflated with nitrogen removing reaction unit in oxygen, ensure that transesterify and/or esterification are carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, controlling temperature of reaction is 170 ~ 230 DEG C, react, until the by product of transesterify and esterification reaches more than 92% of theoretical amount under stirring, condensing condition;
Add the second catalyzer, be evacuated to and be less than 500Pa at 240 ~ 280 DEG C, stir 0.5 ~ 6h, stopped reaction, obtains unsaturated polyester;
In the unsaturated polyester obtained, add a certain amount of initiator, radical polymerization 0.5 ~ 12h at 60 ~ 160 DEG C, obtains product glass reinforced plastic; Wherein, monomer a is selected from aliphatic dibasic acid, binary aliphatic ester or Tetra hydro Phthalic anhydride; Monomer b is aliphatic dihydroxy alcohol; The mass ratio of monomer a and MALEIC ANHYDRIDE is 4:1 ~ 73:49; The mass ratio of monomer b and 2,3-butanediol is 0:1; The mass ratio of the total amount of monomer a and MALEIC ANHYDRIDE and the total amount of monomer b and 2,3-butanediol is 1:1 ~ 1:3; First catalyzer, the second catalyzer account for reactive component a, b, the weight fraction of MALEIC ANHYDRIDE and 2,3-butanediol total amount is 0.001 ~ 0.5%; The weight fraction that initiator accounts for unsaturated polyester is 0.05 ~ 1%;
First catalyzer, the second catalyzer are conventional catalyst transesterify and/or esterification to katalysis, based on following element: the metallic compound of Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La, Ce, Li or Ga.
2. the preparation method of the glass reinforced plastic based on 2,3-butanediol according to claim 1, is characterized in that: the method comprises the following steps:
By monomer a, MALEIC ANHYDRIDE and monomer b, 2,3-butyleneglycol and the first catalyzer join in the flask that whipping appts and condensing works are housed according to a certain percentage, vacuumize, inflated with nitrogen removing reaction unit in oxygen, ensure that transesterify and/or esterification are carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, controlling temperature of reaction is 170 ~ 230 DEG C, react, until the by product of transesterify and esterification reaches more than 92% of theoretical amount under stirring, condensing condition;
Add the second catalyzer, be evacuated to and be less than 500Pa at 240 ~ 280 DEG C, stir 0.5 ~ 6h, stopped reaction, obtains unsaturated polyester;
In the unsaturated polyester obtained, add a certain amount of initiator, radical polymerization 0.5 ~ 12h at 60 ~ 160 DEG C, obtains product glass reinforced plastic;
Wherein, monomer a is selected from aliphatic dibasic acid, binary aliphatic ester or Tetra hydro Phthalic anhydride; Monomer b is aliphatic dihydroxy alcohol; The mass ratio of monomer a and MALEIC ANHYDRIDE is 4:1 ~ 73:49; The mass ratio of monomer b and 2,3-butanediol is 0:1; The mass ratio of the total amount of monomer a and MALEIC ANHYDRIDE and the total amount of monomer b and 2,3-butanediol is 1:1 ~ 1:3; First catalyzer, the second catalyzer account for reactive component a, b, the weight fraction of MALEIC ANHYDRIDE and 2,3-butanediol total amount is 0.001 ~ 0.5%; The weight fraction that initiator accounts for unsaturated polyester is 0.05 ~ 1%;
First catalyzer, the second catalyzer are conventional catalyst transesterify and/or esterification to katalysis, based on following element: the metallic compound of Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La, Ce, Li or Ga.
3. the preparation method of the glass reinforced plastic based on 2,3-butanediol according to claim 2, is characterized in that: the first catalyzer, the second catalyzer account for reactive component a, b, the weight fraction of MALEIC ANHYDRIDE and 2,3-butanediol total amount is 0.005 ~ 0.3%.
4. the preparation method of the glass reinforced plastic based on 2,3-butanediol according to Claims 2 or 3, is characterized in that: described aliphatic dibasic acid is selected from C
2~ C
13straight-chain aliphatic diprotic acid; Described binary aliphatic ester is selected from the C of aliphatic dibasic acid
1-C
6alkyl ester.
5. according to Claims 2 or 3 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 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; Described binary aliphatic ester is selected oneself acid dimethyl.
6. the preparation method of the glass reinforced plastic based on 2,3-butanediol according to Claims 2 or 3, is characterized in that: described aliphatic dibasic acid is selected oneself diacid.
7. the preparation method of the glass reinforced plastic based on 2,3-butanediol according to Claims 2 or 3, is characterized in that: described aliphatic dihydroxy alcohol is selected from C
2~ C
13alkanediol.
8. according to Claims 2 or 3 based on 2, the preparation method of the glass reinforced plastic of 3-butyleneglycol, it is characterized in that: described aliphatic dihydroxy alcohol is selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-PD, neopentyl glycol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane, 1,12-dodecanediol, 1,13-tridecane diols or 2-methyl isophthalic acid, the mixture of one or more in ammediol.
9. the preparation method of the glass reinforced plastic based on 2,3-butanediol according to Claims 2 or 3, is characterized in that: described aliphatic dihydroxy alcohol is selected from BDO or ethylene glycol.
10. the preparation method of the glass reinforced plastic based on 2,3-butanediol according to Claims 2 or 3, is characterized in that: the first described catalyzer is selected from one or both the mixture in titanium compound or acetate; The second described catalyzer is selected from a kind of in titanium compound, tin compound or 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-propyl, titanium isopropylate or the different monooctyl ester of metatitanic acid four or their any mixture; Acetate is selected from a kind of in zinc acetate, magnesium acetate or manganese acetate or their any mixture; Tin compound is selected from a kind of in dibutyltin oxide, dibutyl tin laurate, stannous octoate or tin protochloride or their any mixture; Antimony compounds is selected from one or both the mixture in antimony acetate or antimonous oxide.
11. according to Claims 2 or 3 based on 2, the preparation method of the glass reinforced plastic of 3-butyleneglycol, is characterized in that: described initiator is selected from the one in dilauroyl peroxide, dibenzoyl peroxide, t-butylperoxyl benzoate, di-t-butyl peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The preparation method of 12. glass reinforced plastic based on 2,3-butanediol according to Claims 2 or 3, is characterized in that: described initiator is selected from Diisopropyl azodicarboxylate or dibenzoyl peroxide.
The preparation method of 13. glass reinforced plastic based on 2,3-butanediol according to Claims 2 or 3, is characterized in that: further, adds stopper vacuumizing polycondensation and prepare in the process of unsaturated polyester.
14. is according to claim 13 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.
The preparation method of 15. glass reinforced plastic based on 2,3-butanediol according to claim 13, is characterized in that: described stopper is selected from Resorcinol.
The preparation method of 16. glass reinforced plastic based on 2,3-butanediol according to Claims 2 or 3, is characterized in that: further, after preparing unsaturated polyester, add free yl polymerizating monomer.
17. is according to claim 16 based on 2, the preparation method of the glass reinforced plastic of 3-butyleneglycol, is characterized in that: described free yl polymerizating monomer is selected from the just own ester of vinylbenzene, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, n-BMA or methacrylic acid.
The preparation method of 18. glass reinforced plastic based on 2,3-butanediol according to claim 16, is characterized in that: described free yl polymerizating monomer is selected from vinylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110151855.0A CN102816317B (en) | 2011-06-08 | 2011-06-08 | Glass fiber reinforced plastics based on 2,3-butanediol, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110151855.0A CN102816317B (en) | 2011-06-08 | 2011-06-08 | Glass fiber reinforced plastics based on 2,3-butanediol, and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102816317A CN102816317A (en) | 2012-12-12 |
| CN102816317B true CN102816317B (en) | 2015-05-20 |
Family
ID=47300792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110151855.0A Active CN102816317B (en) | 2011-06-08 | 2011-06-08 | Glass fiber reinforced plastics based on 2,3-butanediol, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102816317B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103804660B (en) * | 2014-03-04 | 2016-02-03 | 中国科学院长春应用化学研究所 | A kind of unsaturated aliphatic-polylactic-acid block copolymer and preparation method thereof |
| CN105482087B (en) * | 2015-12-28 | 2018-06-15 | 肇庆福田化学工业有限公司 | A kind of color inhibition unsaturated polyester resin and its synthetic method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100938431B1 (en) * | 2007-12-28 | 2010-01-25 | (주)디피아이 홀딩스 | Preparing Method Of Unsaturated Polyester Resins Containing Phosphate And Uv-Curing Flame Retarding Paint |
-
2011
- 2011-06-08 CN CN201110151855.0A patent/CN102816317B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102816317A (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101613465B (en) | Weather-proof self-cleaning transparent material and preparation method thereof | |
| CN1250600C (en) | Low melt viscosity amorphous copolymers with enhanced glass transition temperatures | |
| Colomines et al. | Study of the glycolysis of PET by oligoesters | |
| CN107250207B (en) | Bio-based copolyester or copolymerized ethylene terephthalate | |
| CN102516513B (en) | Preparation method of low-yellowing 2,5-furandicarboxylic acid-based polyester | |
| CN101314637A (en) | Poly-p-benzene dicarboxylic acid 1,2-propylene glycol ester and copolyester, and preparation thereof | |
| CN102816317B (en) | Glass fiber reinforced plastics based on 2,3-butanediol, and preparation method thereof | |
| CN104418997A (en) | Synthetic method of polyethylene glycol terephthalate from biomass glycol | |
| CN103992628A (en) | Material capable of realizing ultraviolet-light crosslinking and application thereof to 3D printing material | |
| CN103459457A (en) | Polyester resin resulting from copolymerisation of lactic acid and isosorbide, and production method therefor | |
| CN103159907A (en) | High-molecular-weight polyester plastic based on 2,3-butanediol and preparation method for same | |
| CN102212182A (en) | Curing agent methylene diphenyl diisocyanate tripolymer and method for preparing same | |
| CN102864022B (en) | Soybean oil maleic acid monoester, and preparation method and application thereof | |
| Bamane et al. | Replacement of traditional unsaturated acid by bio-based itaconic acid in the preparation of isophthalic acid-based unsaturated polyester resin | |
| CN102775586B (en) | Novel polyester-polyether polyatomic alcohol and preparation method thereof | |
| CN102786657B (en) | Preparation method and application of biomass base bi-component polyurethane | |
| CN111978444B (en) | Organic polyacid-based photocuring resin and preparation method and application thereof | |
| CN101712751B (en) | Method for synthesizing unsaturated polyester | |
| CN102766326B (en) | Polyurethane foaming plastic and its preparation method | |
| Tan et al. | Direct transformation of fatty acid-derived monomers from dimer acid manufacturing into valuable bio-plasticizers with high plasticization and compatibilization | |
| CN103237830B (en) | The unsaturated polyester resin of modification by acid and alkoxide component with lactic acid replacement polyester | |
| CN103435774B (en) | Method for modifying polyester bioelastomer | |
| CN102585180B (en) | Copolyester based on 2, 3-butanediol and preparation method thereof | |
| JP6891491B2 (en) | Polyester resin | |
| CN103342780B (en) | Method for preparing high-strength polyurethane by use of unsaturated resin and styrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Correlation module identifying method based on 2-type heterogeneous network Effective date of registration: 20191202 Granted publication date: 20150520 Pledgee: Chuzhou economic and Technological Development Corporation Pledgor: Shanghai Jieshijie New Materials (Group) Co., Ltd. Registration number: Y2019980000815 |