CN114349948B - Preparation method of catalyst and preparation method of chlorine-containing unsaturated polyester - Google Patents
Preparation method of catalyst and preparation method of chlorine-containing unsaturated polyester Download PDFInfo
- Publication number
- CN114349948B CN114349948B CN202210036866.2A CN202210036866A CN114349948B CN 114349948 B CN114349948 B CN 114349948B CN 202210036866 A CN202210036866 A CN 202210036866A CN 114349948 B CN114349948 B CN 114349948B
- Authority
- CN
- China
- Prior art keywords
- acid
- unsaturated polyester
- catalyst
- preparation
- product
- 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
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a catalyst and a preparation method of chlorine-containing unsaturated polyester. The preparation method of the catalyst comprises the following steps: the preparation method comprises the steps of using a solution compounded by polyamide acid, solid acid and a biphthalimide monomer, carrying out imidization process of acetic anhydride and organic base, and then crushing, washing and vacuum drying in an aqueous solution by using a wet crusher to prepare the catalyst with the porous structure of the polyimide carrier. The preparation method of the chlorine-containing unsaturated polyester comprises the following steps: refluxing and dehydrating the chloro-o-xylene vapor phase oxidation by-product and dihydric alcohol in a solvent, and adding a catalyst to prepare an unsaturated polyester solution; and after dehydration, cooling the solution, adding active carbon for decolorization, filtering, and evaporating the solvent to obtain the unsaturated polyester. The application problem of the by-product can be effectively solved, and the problem of solid waste of the production line is solved. The flame retardancy and heat resistance of the cured unsaturated polyester resin are improved.
Description
Technical Field
The invention relates to polyester, in particular to a catalyst for chlorine-containing unsaturated polyester, a method thereof and a preparation method of the chlorine-containing unsaturated polyester.
Background
The chlorophthalic anhydride is an important solid monomer for synthesizing polyimide, and can be used for synthesizing monomers such as biphenyl dianhydride, benzophenone dianhydride, diphenyl ether dianhydride, triphenyl diether dianhydride, diphenyl sulfide dianhydride, bisphenol A diether dianhydride, bischloro diphthalic imide and the like, and further synthesizing polyimide with various structures.
At present, the mainstream synthesis method of chlorophthalic anhydride mainly comprises the steps of preparing 3 (4) -mixed chloro-o-xylene (the proportion is about 45. The oxidation process is the core process of the process. The oxidation is divided into two modes: gas phase oxidation and liquid phase oxidation. Among them, documents CN1257867A, CN1324793A, etc. introduce a gas phase oxidation method, i.e. chloro-o-xylene and compressed air are subjected to gas phase oxidation at a certain ratio at a temperature of 300-400 ℃, and the product is collected and melted by a condenser, and then is rectified to remove moisture, and chloro-phthalic anhydride is separated to prepare the finished product. The other part of the by-products generated by oxidation enter another link, and the by-products are obtained after treatment, wherein the by-products comprise maleic acid, fumaric acid, chloromaleic acid, chloromalemaleic acid, mesaconic acid, phthalic acid, 3-chlorophthalic acid, 4-chlorophthalic acid and p-chlorobenzoic acid. The substance is a chlorine-containing mixed dibasic acid. Has no practical utilization value and can only be treated as solid waste.
Disclosure of Invention
In view of the above, the present invention is directed to the development of a process for the use of chloro-o-xylene vapor phase oxidation by-products in combination with glycols to produce chlorine-containing unsaturated polyesters.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a catalyst for preparing chlorine-containing unsaturated polyester comprises the following steps: the preparation method comprises the steps of using a solution compounded by polyamide acid, solid acid and a biphthalimide monomer, carrying out imidization process of acetic anhydride and organic base, and then crushing, washing and vacuum drying in an aqueous solution by using a wet crusher to prepare the catalyst with the porous structure of the polyimide carrier.
In the catalyst of the invention, polyimide is used as a catalyst carrier, solid acid plays a role of the catalyst, and the solid acid is embedded into the pore diameter of the polyimide under the function of the biphthalimide.
A preparation method of chlorine-containing unsaturated polyester comprises the following steps: refluxing and dehydrating the chloro-o-xylene vapor phase oxidation by-product and dihydric alcohol in a solvent, and adding the catalyst to prepare an unsaturated polyester solution; and after dehydration, cooling the solution, adding active carbon for decolorization, filtering, and evaporating the solvent to obtain the unsaturated polyester.
The preparation method of the polyamic acid comprises the following steps: aromatic dianhydride and alicyclic diamine are polymerized in an aprotic polar solvent to prepare polyamic acid.
The aromatic dianhydride of the present invention comprises one or more of pyromellitic dianhydride, biphenyl dianhydride, benzophenone dianhydride, diphenyl ether dianhydride, etc.
The alicyclic diamine comprises isophorone diamine, 1, 4-cyclohexanediamine and H 12 MDA, and the like.
The molar ratio of the aromatic dianhydride to the alicyclic diamine is 1:0.98-1:1.02.
in the preparation method of the catalyst, the solvent used comprises one or more of N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and the like.
In the preparation method of the catalyst, the mass ratio of the sum of the mass of the aromatic dianhydride and the alicyclic diamine to the solvent is 10/90-30/70.
The solid acid is one or more of sebacic acid, undecanedioic acid and dodecanedioic acid.
The mass of the solid acid is 2-10% of the sum of the mass of the aromatic dianhydride and the mass of the alicyclic diamine.
The bisphthalimide monomers of the present invention are a class of N-phenyl-N' -phenyl bisphthalimide monomers, suitable examples include, but are not limited to, those of formula a:
formula B:
and formula C: />
The dosage of the biphthalimide monomer is 3-12 times of the mass of the solid acid.
In the preparation method of the catalyst, the catalyst used in the imidization reaction is acetic anhydride, and the addition amount of the acetic anhydride is 1-5 per mill of the sum of the mass of the aromatic dianhydride and the mass of the alicyclic diamine.
The organic base is triethylamine, pyridine, picoline and the like, and the addition amount is 1-5 per mill of the mass sum of dianhydride and diamine.
In the preparation method of the catalyst, water used for crushing the solution by a wet crusher is 3-15 times of the mass of the solvent; filtering the solid obtained after crushing, washing the solid with boiled water with 8 to 20 times of the sum of the mass of the aromatic dianhydride and the alicyclic diamine (namely the mass of the generated polyamic acid), and drying the solid in absolute pressure at 140 to 160 ℃ under vacuum to obtain the catalyst.
The main components of the by-product of the gas phase oxidation of the chloro-o-xylene comprise 4-chlorophthalic acid, 3-chlorophthalic acid, maleic acid, fumaric acid, chloro-maleic acid, chloro-fumaric acid, mesaconic acid, phthalic acid, p-chlorobenzoic acid and the like. Preferred compositions are as in table 1 below:
TABLE 1 chloro-o-xylene gas phase oxidation by-product composition
The dihydric alcohol of the present invention includes, but is not limited to, one or more of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, diethylene glycol, triethylene glycol, and the like.
In the method for preparing chlorine-containing unsaturated polyester, the solvent is high boiling point non-polar solvent, preferably one or more of aliphatic hydrocarbon and aromatic hydrocarbon with boiling point of 125-175 ℃, and suitable examples include but are not limited to one or more of ethylbenzene, xylene, o-xylene, trimethylbenzene, chlorobenzene, n-nonane and n-decane.
In the preparation method of the chlorine-containing unsaturated polyester, the dosage ratio of the chloro-o-xylene gas phase oxidation by-product to the dihydric alcohol is 100:98 to 102, calculated as the molar ratio of carboxyl in the chloro-o-xylene gas phase oxidation by-product to hydroxyl in the dihydric alcohol.
In the method for preparing the chlorine-containing unsaturated polyester, the mass ratio of the sum of the mass of the chloro-o-xylene vapor phase oxidation by-product and the mass of the dihydric alcohol to the mass of the high-boiling-point nonpolar solvent is (2.
In the preparation method of the chlorine-containing unsaturated polyester, the dosage of the catalyst is 1-10% of the mass of the chloro-o-xylene gas-phase oxidation by-product.
In the preparation method of the chlorine-containing unsaturated polyester, the temperature of reflux dehydration is 130-180 ℃.
In the preparation method of the chlorine-containing unsaturated polyester, the temperature is reduced to 60-80 ℃ after dehydration is finished.
In the preparation method of the chlorine-containing unsaturated polyester, the mass of the added active carbon is 1/10-1/6 of the sum of the mass of the chloro-o-xylene gas phase oxidation by-product, the mass of the dihydric alcohol and the mass of the high-boiling-point nonpolar solvent.
In the preparation method of the chlorine-containing unsaturated polyester, the decoloring time is 0.5 to 5 hours.
In the preparation method of the chlorine-containing unsaturated polyester, the method for distilling the solvent is negative pressure distillation, and the vacuum degree is gage pressure of minus 0.095 to minus 0.1MPa; the distillation temperature is-85 to-130 ℃.
The structure of the chlorine-containing unsaturated polyester is shown as follows:
wherein R and R' are independently selected from- (CH) 2 ) 2 -、-(CH 2 ) 3 -、-(CH 2 ) 2 -O-(CH 2 ) 2 -、-(CH 2 ) 2 -O-(CH 2 ) 2 -O-(CH 2 ) 2 -; r 'and R' are independently H or Cl.
The invention has the beneficial effects that:
1. the invention utilizes the chloro-o-xylene gas phase oxidation by-product to carry out and unsaturated polyester, can effectively solve the application problem of the by-product, and solves the problem of solid waste of a production line;
2. in the conventional synthesis of unsaturated polyesters, no catalyst is usually used. However, the method has the problems that the reaction process is long, and the average synthesis time per kettle is more than 16 hours; the molecular weight of the long-chain polymer is controlled by sampling the reaction process to measure the acid number. Due to the operation deviation of operators, unstable conditions are easy to occur in reaction batches, which are usually expressed by too wide molecular weight distribution and the like; after the catalyst is used, the reaction time can be increased to 8-12 hours, and the reaction time is greatly shortened; in addition, the molecular weight distribution of the product is narrow due to the use of the catalyst. This may be associated with the uniform dispersion of the catalyst in the system, resulting in an increase in the concentration uniformity throughout the system, thereby reducing the effect of mass transfer on the concentration in the system;
3. the catalyst prepared by the method is a porous catalyst, and the biphthalimide and the solid acid of the catalyst are both dispersed in the pore channels of the catalyst, wherein the biphthalimide can change and reduce the toughness of the polyimide, so that the polyimide can be more easily crushed into powder; solid acid is used as a catalyst and embedded in the porous structure of the polyimide, so that the catalyst can be prevented from being dissolved in unsaturated polyester and can be easily separated out;
4. the synthesized unsaturated polyester contains chlorine, and the flame retardance and the heat resistance of the cured unsaturated polyester resin are improved.
5. The unsaturated polyester synthesized by the traditional method does not adopt a nonpolar solvent. However, a part of the formed water was not distilled off to cause hydrolysis of the formed ester group. The invention adopts the non-polar solvent for reflux, and can ensure that moisture and redundant inorganic acid can be discharged out of the system. Furthermore, the molecular weight is controlled by the molar ratio, so that the stability of the reaction batch can be ensured.
Detailed Description
The present invention is further illustrated by the following examples, which are provided only for the purpose of illustration and are not intended to limit the scope of the present invention.
The composition of the by-product of the gas phase oxidation of chloro-o-xylene used in the following examples is shown in Table 2:
table 2: examples by-product main component of gas phase oxidation of chloro-o-xylene
Example 1
Preparing a catalyst:
adding 21.8g of pyromellitic dianhydride, 16.66g of isophorone diamine and 346g of DMAC (dimethylacetamide) into a 2000ml three-neck flask, starting stirring, and stirring for dissolving until the viscosity is not increased any more to obtain a polyamic acid solution; 0.77g of sebacic acid and 2.31g of N-phenyl-N' -phenyl-diphthalic imide having the structure of the formula A were added to the solution, and after stirring was continued until dissolved, 0.04g of acetic anhydride and 0.04g of pyridine were added, and stirring was continued for 3 hours to prepare a polyimide solution. The polyimide solution was mixed with 1038g of water and pulverized with a wet pulverizer, and the resulting solid was filtered and washed 4 times with boiling water, 308g of water each time. The solid obtained after washing was dried under vacuum at 140 ℃ for 24 hours under absolute pressure to obtain catalyst a.
Preparing resin:
a condensation pipe, a water separator and a stirrer are connected on a 1000ml three-neck flask, 100g of chloro-o-xylene vapor phase oxidation by-product, 30g of ethylene glycol and 45.9g1, 2-propylene glycol are added into the flask, 236.85g of n-nonane and 1g of catalyst a are added; filling nitrogen for replacement, starting stirring and heating. When the system is heated to 130 ℃, the n-nonane starts to flow back, and water is gradually distributed in the water separator. When no water drop falls in the water separator, stopping heating, reducing the temperature of the system to 60 ℃, adding 17.59g of activated carbon into the reaction kettle, decoloring for 0.5h, filtering the system, and filtering out the activated carbon.
The filtrate was added to a vacuum distillation still, the solvent was distilled off at-0.095 MPa and 85 ℃ and the unsaturated polyester 156g was obtained by cooling.
The unsaturated polyester product was mixed with 52g of styrene (product 1/3 mass) and 0.16g of hydroquinone (product 1 ‰ mass) to give an unsaturated polyester resin product. And solidifying and molding after the product is solidified. The Tg was measured to be 205 ℃. The limiting oxygen index is 26%. The whole reaction time is 8 hours.
Example 2
Preparing a catalyst:
adding 29.4g of biphenyl dianhydride, 16.83g of isophorone diamine and 262g of DMF into a 2000ml three-neck flask, starting stirring, and stirring to dissolve until the viscosity is not increased any more to obtain a polyamic acid solution; 1.85g of dodecanedioic acid and 9.25g of N-phenyl-N' -phenyl diphthalic imide having the structure of the formula B were added to the solution, and after stirring was continued until dissolved, 0.09g of acetic anhydride and 0.09g of pyridine were added, and stirring was continued for 3 hours to prepare a polyimide solution. The polyimide solution was mixed with 1048g of water and pulverized with a wet pulverizer, and the resulting solid was filtered and washed 4 times with 462g of water each time with boiling water. The solid obtained after washing was dried under vacuum at 145 ℃ for 24 hours under an absolute pressure to obtain catalyst b.
Preparing resin:
connecting a condenser pipe, a water separator and a stirrer on a 1000ml three-neck flask, adding 100g of chloro-o-xylene gas phase oxidation by-product, 25g of ethylene glycol and 63.61g of 1, 4-butanediol into the flask, adding 188.61g of o-xylene, and adding 2g of catalyst b; filling nitrogen for replacement, starting stirring and heating. When the system is heated to 150 ℃, the solvent begins to flow back, and water is gradually distributed in the water separator. When no water drops fall in the water separator, stopping heating, reducing the temperature of the system to 65 ℃, adding 23.58g of activated carbon into the reaction kettle, decoloring for 1 hour, filtering the system, and filtering out the activated carbon.
The filtrate is added into a vacuum distillation still, n-nonane is distilled out under the pressure of-0.097 MPa and at the temperature of 115 ℃, and 169g of unsaturated polyester is obtained after the temperature is reduced.
The unsaturated polyester was mixed with 56g of styrene (1/3 mass of the product) and 0.17g of hydroquinone (1 ‰ mass of the product) to give an unsaturated polyester resin product. And solidifying and molding after the product is solidified. The Tg was tested to be 213 ℃. The limiting oxygen index is 25%. The whole reaction time was 9 hours.
Example 3
Preparing a catalyst:
adding 32.2g of benzophenone dianhydride, 11.286g of 1, 4-cyclohexanediamine and 174g of NMP into a 2000ml three-neck flask, starting stirring, and stirring to dissolve until the viscosity is not increased any more to obtain a polyamic acid solution; 2.61g of dodecanedioic acid and 20.87g of N-phenyl-N' -phenyl diphthalic imide having the structure of the formula A were added to the solution, and after stirring was continued until dissolved, 0.13g of acetic anhydride and 0.13g of pyridine were added, and stirring was continued for 3 hours to prepare a polyimide solution. The polyimide solution was mixed with 1739g of water and pulverized by a wet pulverizer, and the resulting solid was filtered and washed 4 times with boiling water, 522g of water each time. The solid obtained after washing was dried under vacuum at 150 ℃ for 24 hours under absolute pressure to obtain catalyst c.
Preparing resin:
connecting a condenser pipe, a water separator and a stirrer on a 1000ml three-neck flask, adding 100g of chloro-o-xylene vapor phase oxidation by-product, 30g of diethylene glycol and 75.43g of 1, 4-butanediol into the flask, adding 102.72g of trimethylbenzene, and adding 5g of catalyst c; filling nitrogen for replacement, starting stirring and heating. When the system is heated to 160 ℃, the solvent begins to flow back, and water is gradually distributed in the water segregator. When no water drops fall in the water separator, stopping heating, reducing the temperature of the system to 70 ℃, adding 29.35g of activated carbon into the reaction kettle, decoloring for 2 hours, filtering the system, and filtering out the activated carbon.
The filtrate is added into a vacuum distillation still, the solvent is distilled off under-0.098 MPa and at 130 ℃, and the unsaturated polyester 185g is obtained after cooling.
The unsaturated polyester was mixed with 62g of styrene (1/3 mass of the product) and 0.19g of hydroquinone (1 ‰ mass of the product) to produce an unsaturated polyester resin finished product. And solidifying and forming after the product is solidified. The Tg was tested to be 206 ℃. The limiting oxygen index is 27%. The whole reaction time is 10 hours.
Example 4
Preparing a catalyst:
adding 31g of diphenyl ether dianhydride, 21.21gH12MDA and 157gDMSO into a 2000ml three-neck flask, starting stirring, and stirring and dissolving until the viscosity is not increased any more to obtain a polyamic acid solution; 4.18g of undecanedioic acid and 41.8g of N-phenyl-N' -phenylbiphthalimide of the formula C were added to the solution, and after stirring was continued until dissolved, 0.21g of acetic anhydride and 0.21g of triethylamine were added, and stirring was continued for 3 hours to prepare a polyimide solution. The polyimide solution was mixed with 1880g of water and pulverized with a wet pulverizer, and the resulting solid was filtered and washed 4 times with boiling water, 783g of water each time. The solid obtained after washing was dried under vacuum at 155 ℃ for 24 hours under an absolute pressure to obtain catalyst d.
Preparing resin:
a condenser, a water separator and a stirrer were connected to a 1000ml three-necked flask, and 100g of a by-product of vapor phase oxidation of chloro-o-xylene, 30g2, 3-butanediol, 30g1, 4-butanediol and 30g1, 2-butanediol, 63.33g of n-decane and 7g of catalyst d were added to the flask, and then the flask was purged with nitrogen, stirred and heated. When the system is heated to 180 ℃, the solvent begins to flow back, and water is gradually distributed in the water segregator. When no water drops fall in the water separator, stopping heating, reducing the temperature of the system to 75 ℃, adding 17.78g of activated carbon into the reaction kettle, decoloring for 4 hours, filtering the system, and filtering out the activated carbon.
And adding the filtrate into a vacuum distillation kettle, evaporating the solvent at-0.099 MPa and 140 ℃, and cooling to obtain 140g of unsaturated polyester.
The unsaturated polyester was mixed with 47g of styrene (1/3 mass of the product) and 0.14g of hydroquinone (1 ‰ mass of the product) to give an unsaturated polyester resin product. And solidifying and forming after the product is solidified. The Tg was measured to be 194 ℃. The limiting oxygen index is 24%. The whole reaction time is 11 hours
Example 5
Preparing a catalyst:
adding 21.8g of pyromellitic dianhydride, 21.42g of H12MDA and 101g of DMAC into a 2000ml three-neck flask, starting stirring, and stirring and dissolving until the viscosity is not increased any more to obtain a polyamic acid solution; 4.32g of undecanedioic acid and 51.86g of N-phenyl-N' -phenylbisphthalimide having the structure of the formula C were added to the solution, and after stirring was continued until dissolved, 0.22g of acetic anhydride and 0.22g of picoline were added, and stirring was continued for 3 hours to prepare a polyimide solution. The polyimide solution was mixed with 1513g of water and pulverized with a wet pulverizer, and the obtained solid was filtered and washed 4 times with boiling water, 864g of water each time. The solid obtained after washing was dried under an absolute pressure at 160 ℃ for 24 hours to obtain catalyst e.
Preparing resin:
a condenser, a water separator and a stirrer are connected to a 1000ml three-neck flask, 100g of chloro-o-xylene vapor phase oxidation by-product, 86.05g of 1, 2-propylene glycol, 53.16g of xylene are added to the flask, 10g of catalyst e is added, nitrogen is filled for replacement, stirring is started, and heating is carried out. When the system is heated to 145 ℃, the solvent begins to flow back, and water is gradually distributed in the water separator. When no water drop falls in the water separator, stopping heating, reducing the temperature of the system to 80 ℃, adding 31.00g of activated carbon into the reaction kettle, decoloring for 5 hours, filtering the system, and filtering out the activated carbon.
Adding the filtrate into a vacuum distillation kettle, distilling off the solvent at-0.1 MPa and 90 ℃, and cooling to obtain 166g of unsaturated polyester.
The unsaturated polyester is mixed with 55g of styrene (product 1/3 mass) and 0.17g of hydroquinone (product 1 ‰ mass) to produce the unsaturated polyester resin finished product. And solidifying and forming after the product is solidified. The Tg was tested to be 208 ℃. The limiting oxygen index is 27%. The whole reaction time is 12 hours.
Comparative example 1
For comparison, example 2 is used. The hydrochloric acid in 100g of the by-product of the vapor phase oxidation of chloro-o-xylene in example 2 was replaced with perchloric acid in the same molar ratio, i.e., chlorophthalic acid was replaced with equimolar phthalic acid, chloromaleic acid was replaced with equimolar maleic acid, chloromaleic acid was replaced with equimolar fumaric acid, chloromethylmesaconic acid was replaced with equimolar mesaconic acid, and chlorobenzoic acid was replaced with equimolar benzoic acid. The compositions are as follows in table 3:
table 3: comparative example 1 gas phase oxidation of by-product of o-xylene chloride
Catalyst:
the catalyst of this comparative example was prepared as described in example 2.
Preparing resin:
connecting a condenser, a water separator and a stirrer on a 1000ml three-neck flask, adding 25g of ethylene glycol and 63.61g of 1, 4-butanediol according to the raw materials in the table 3 into the flask, adding 188.61g of o-xylene, and adding 2g of a catalyst b; filling nitrogen for replacement, starting stirring and heating. When the system is heated to 150 ℃, the solvent begins to flow back, and water is gradually distributed in the water separator. When no water drops fall in the water separator, stopping heating, reducing the temperature of the system to 65 ℃, adding 23.58g of activated carbon into the reaction kettle, decoloring for 1 hour, filtering the system, and filtering out the activated carbon.
The filtrate is added into a vacuum distillation still, n-nonane is evaporated under-0.097 MPa and at 115 ℃, and 169g of unsaturated polyester is obtained by cooling.
The unsaturated polyester is mixed with 56g of styrene (product 1/3 mass) and 0.17g of hydroquinone (product 1 ‰ mass) to produce the unsaturated polyester resin finished product. And solidifying and forming after the product is solidified. The Tg was tested to be 176 ℃. The limiting oxygen index is 18%. The entire reaction time was 9 hours.
This comparative example shows that the chlorine-containing unsaturated polyester resin is inferior in flame retardancy and heat resistance to the chlorine-free unsaturated polyester resin.
Comparative example 2
For comparison, example 2 is used. The starting materials from example 2 were polymerized without addition of catalyst. And solidifying and forming after the product is solidified. The Tg was tested to be 213 ℃. The limiting oxygen index is 25%. The whole reaction time is 16 hours.
This comparative example illustrates that the reaction time is shorter with the catalyst of the invention than without the catalyst.
Comparative example 3
A condenser, a water separator and a stirrer were connected to a 1000ml three-necked flask, and 100g of a vapor phase oxidation by-product of chloro-o-xylene, 25g of ethylene glycol, 63.61g of 1, 4-butanediol and 2g of the catalyst b in example 2 were added to the flask; filling nitrogen for replacement, starting stirring and heating. When the system was heated to 160 ℃, the water formed was gradually distilled off. When no water drops fall in the water separator, stopping heating, reducing the temperature of the system to 65 ℃, adding 23.58g of activated carbon into the reaction kettle, decoloring for 1 hour, filtering the system, and filtering out the activated carbon. 169g of unsaturated polyester was obtained.
The unsaturated polyester was mixed with 56g of styrene (1/3 mass of the product) and 0.17g of hydroquinone (1 ‰ mass of the product) to give an unsaturated polyester resin product. And solidifying and forming after the product is solidified. The Tg was tested to be 210 ℃. The limiting oxygen index is 23%. The whole reaction time was 9 hours.
In comparative example 3, water removal was not performed by solvent-borne water. This results in incomplete water removal and the water formed in turn hydrolyzes the ester groups formed and leads to a reduction in the molecular weight. Therefore, the unsaturated polyester resin product prepared by this comparative example had both a lower Tg and a lower limiting oxygen index than comparative example 2.
Comparative example 4
Connecting a condenser pipe, a water separator and a stirrer on a 1000ml three-neck flask, adding 100g of chloro-o-xylene gas phase oxidation by-product, 25g of ethylene glycol, 63.61g of 1, 4-butanediol and 188.61g of o-xylene into the flask; filling nitrogen for replacement, starting stirring and heating. When the system is heated to 150 ℃, the solvent begins to flow back, and water is gradually distributed in the water separator. When no water drops fall in the water separator, stopping heating, reducing the temperature of the system to 65 ℃, adding 23.58g of activated carbon into the reaction kettle, decoloring for 1 hour, filtering the system, and filtering out the activated carbon.
The filtrate is added into a vacuum distillation still, n-nonane is distilled out under the pressure of-0.097 MPa and at the temperature of 115 ℃, and 169g of unsaturated polyester is obtained after the temperature is reduced.
The unsaturated polyester was mixed with 56g of styrene (1/3 mass of the product) and 0.17g of hydroquinone (1 ‰ mass of the product) to give an unsaturated polyester resin product. And solidifying and forming after the product is solidified. The Tg was tested to be 213 ℃. The limiting oxygen index is 25%. The whole reaction time is 16 hours.
In comparative example 4, no catalyst was added during the polymerization. Therefore, the unsaturated polyester resin prepared by this comparative example has a longer polymerization time than example 2.
Comparative example 5
For comparison, example 2 is used. The solid acid was not added in the step of preparing the catalyst in example 2, and the system was catalyzed and polymerized. And solidifying and forming after the product is solidified. The Tg was tested to be 213 ℃. The limiting oxygen index is 26%. The whole reaction time is 16 hours. This comparative example illustrates that the bis-phthalimide in the catalyst of the present invention has no catalytic effect on the polymerization.
Comparative example 6
Example 2 is used for comparison. The system was catalyzed and polymerized without adding biphthalimide to the catalyst preparation step of example 2. And solidifying and forming after the product is solidified. The Tg was tested to be 213 ℃. The limiting oxygen index is 26%. The whole reaction time was 13 hours.
This comparative example illustrates that the solid acid in the catalyst of the present invention exerts a certain catalytic effect on the polymerization. In the comparative example, no bisphthalimide was added, so that the solid acid could not be inserted into the pore diameter of the polyimide, and the polymerization system was turbid.
Comparative example 7
Example 2 is used for comparison. In the step of preparing the catalyst in the example 2, the solid acid and the diphthalimide are not added, and the system is catalyzed and polymerized. And solidifying and molding after the product is solidified. The Tg was tested to be 213 ℃. The limiting oxygen index is 26%. The whole reaction time is 16 hours.
This comparative example illustrates that the polyimide in the catalyst of the present invention has no catalytic effect on the polymerization.
Claims (10)
1. A preparation method of a catalyst for preparing chlorine-containing unsaturated polyester comprises the following steps: the preparation method comprises the steps of using solution compounded by polyamide acid, solid acid and a biphthalimide monomer, carrying out imidization process of acetic anhydride and organic base, crushing in aqueous solution by using a wet crusher, washing, and drying in vacuum to prepare the catalyst with the porous structure of the polyimide carrier.
2. The method of claim 1, wherein: the preparation method of the polyamic acid comprises the following steps: polymerizing aromatic dianhydride and alicyclic diamine in an aprotic polar solvent; the aromatic dianhydride comprises one or more of pyromellitic dianhydride, biphenyl dianhydride, benzophenone dianhydride and diphenyl ether dianhydride; the alicyclic diamine comprises isophorone diamine, 1, 4-cyclohexanediamine and H 12 One or more of MDA.
3. The method according to claim 1 or 2, characterized in that the solid acid is one or more of sebacic acid, undecanedioic acid, dodecandioic acid.
4. The method according to claim 2 or 3, wherein the mass of the solid acid is 2 to 10% of the sum of the mass of the aromatic dianhydride and the mass of the alicyclic diamine.
5. The method of any one of claims 1 to 4, wherein the bis-phthalimide monomer is of formula A:
formula B: />
And formula C:
one or more of (a).
6. The method according to any one of claims 1 to 5, wherein the amount of the bisphthalimide monomer is 3 to 12 times the mass of the solid acid.
7. A method for preparing chlorine-containing unsaturated polyester comprises the following steps: refluxing and dehydrating chloro-o-xylene vapor phase oxidation by-product and dihydric alcohol in a solvent, and adding the catalyst prepared by the method of any one of claims 1 to 6 to prepare an unsaturated polyester resin solution; and after dehydration, cooling the solution, adding active carbon for decolorization, filtering, and evaporating the solvent to obtain the unsaturated polyester.
8. The process according to claim 7, characterized in that said chloro-ortho-xylene gas-phase oxidation by-products comprise the following composition: 0 to 0.5 percent of maleic acid, 3.0 to 10.0 percent of fumaric acid, 0.1 to 0.6 percent of chloro maleic acid, 3.0 to 10.0 percent of chloro fumaric acid, 2.0 to 6.0 percent of mesaconic acid, 0.1 to 0.8 percent of phthalic acid, 32.0 to 38.0 percent of 3-chlorophthalic acid, 35.0 to 46.0 percent of 4-chlorophthalic acid and 0 to 1.0 percent of p-chlorobenzoic acid.
9. The method according to claim 7 or 8, wherein the diol is selected from one or more of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, diethylene glycol, triethylene glycol.
10. The process according to any one of claims 7 to 9, wherein the catalyst is used in an amount of 1 to 10% by mass based on the amount of the by-product of the gas phase oxidation of chloro-o-xylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210036866.2A CN114349948B (en) | 2022-01-13 | 2022-01-13 | Preparation method of catalyst and preparation method of chlorine-containing unsaturated polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210036866.2A CN114349948B (en) | 2022-01-13 | 2022-01-13 | Preparation method of catalyst and preparation method of chlorine-containing unsaturated polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114349948A CN114349948A (en) | 2022-04-15 |
| CN114349948B true CN114349948B (en) | 2023-04-07 |
Family
ID=81108594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210036866.2A Active CN114349948B (en) | 2022-01-13 | 2022-01-13 | Preparation method of catalyst and preparation method of chlorine-containing unsaturated polyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114349948B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1945626A1 (en) * | 1968-09-09 | 1970-03-26 | Nippon Catalytic Chem Ind | Process for the production of unsaturated polyester resin |
| CN102617877A (en) * | 2012-04-10 | 2012-08-01 | 中国科学院长春应用化学研究所 | Preparation method for polyimide film |
| CN108929438A (en) * | 2017-05-23 | 2018-12-04 | 万华化学集团股份有限公司 | A kind of preparation method of polyamic acid and the method that polyimides is prepared by the polyamic acid |
-
2022
- 2022-01-13 CN CN202210036866.2A patent/CN114349948B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1945626A1 (en) * | 1968-09-09 | 1970-03-26 | Nippon Catalytic Chem Ind | Process for the production of unsaturated polyester resin |
| CN102617877A (en) * | 2012-04-10 | 2012-08-01 | 中国科学院长春应用化学研究所 | Preparation method for polyimide film |
| CN108929438A (en) * | 2017-05-23 | 2018-12-04 | 万华化学集团股份有限公司 | A kind of preparation method of polyamic acid and the method that polyimides is prepared by the polyamic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114349948A (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Synthesis and properties of phthalonitrile-terminated oligomeric poly (ether imide) s containing phthalazinone moiety | |
| JP6074443B2 (en) | Preparation method of polyimide | |
| JPH01123827A (en) | High capacity heterocyclic oligomer and blend | |
| JP2698774B2 (en) | Poly (imide-amic acid ester) and method for producing the same, and polyimide, polyimide film, polyimide fiber and method for producing the same using the same | |
| CN114349948B (en) | Preparation method of catalyst and preparation method of chlorine-containing unsaturated polyester | |
| Liaw et al. | Synthesis and characterization of new poly (amide–imide) s from 1, 4‐bis (4‐trimellitimidophenoxy)‐2‐tert‐butylbenzene with various diamines | |
| US5120825A (en) | Polymers containing both imidazole and imidazolone structural units | |
| JP3012903B2 (en) | New soluble polyimide resin | |
| WO1992001678A1 (en) | Heat resistant polyimide - benzoxazole polymers and composites thereof | |
| JPH02142830A (en) | Copolyimide obtained from 2-(3-aminophenyl)- 2-(4-aminophenyl)hexafluoropropane | |
| Sakaguchi et al. | Synthesis of polyimide and poly (imide‐benzoxazole) in polyphosphoric acid | |
| JP2017132845A (en) | Method for producing polyimide molding | |
| US5280103A (en) | Perfluoroalkylated amines, and polymers made therefrom | |
| CN103408521B (en) | A kind of polymerization-grade 4, method for making of 4 '-paraphenylene terephthalamide diphthalic anhydrides and products thereof and purposes | |
| US4978742A (en) | Polymers prepared from 2-(3-aminophenyl)-2-(4-aminophenyl) hexafluoro propane | |
| JPS6339616B2 (en) | ||
| EP0644870B1 (en) | Perfluoroalkylated diaminomesitylene and polyimides therefrom | |
| US6274699B1 (en) | Polyimides and process for preparing polyimides having thermal-oxidative stability | |
| Yang et al. | Syntheses and properties of organosoluble polyamides and polyimides based on the diamine 3, 3‐bis [4‐(4‐aminophenoxy)‐3‐methylphenyl] phthalide derived from o‐cresolphthalein | |
| KR20010038350A (en) | Unsymmetric Diamine Monomer Having Trifluoromethyl and Soluble Aromatic Polyimides Prepared by Using the Same | |
| CN110256670B (en) | Thermoplastic polyimide containing fluorene group and preparation method and application thereof | |
| JP3901164B2 (en) | Aromatic polyamideimide and its precursor | |
| Wang et al. | Preparation and characterization of low degree of branching aromatic polyamides from a new BB’B’’triamine monomer and dicarboxylic acids | |
| US5047499A (en) | Process for the production of high molecular weight polyamide-imide resin | |
| CN117304484A (en) | Polyimide prepolymer resin containing silicon and Cardo structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |