WO2015070606A1

WO2015070606A1 - Catalytic system for catalyzing ring opening polymerization of tetrahydrofuran

Info

Publication number: WO2015070606A1
Application number: PCT/CN2014/080215
Authority: WO
Inventors: 郭桦; 梅雪; 徐冬; 于家琳; 陈昊然
Original assignee: 国电新能源技术研究院
Priority date: 2013-11-14
Filing date: 2014-06-18
Publication date: 2015-05-21
Also published as: CN103554464A

Abstract

The present invention relates to a catalytic system for catalyzing the ring opening polymerization of tetrahydrofuran, comprising perfluorinated sulfonic acid resin. The chemical general formula of the perfluorinated sulfonic acid resin is Formula(I). x is 4 to 12, y is 1, z is 0, 1, or 2, n is 0 to 5, R is F, ONa, or OH; and the perfluorinated sulfonic acid resin contains 10% to 30% by weight of separable substance. The present invention is characterized in that the catalytic system can be recovered and reused; the entire production process of polytetramethylene ether glycol (PTMEG) has the advantages of few byproduct varieties, low output, simple process, and low energy consumption.

Description

Catalytic system for catalyzing ring-opening polymerization of tetrahydrofuran

Technical field

The invention relates to a catalytic system for catalyzing ring-opening polymerization of tetrahydrofuran. The catalyst can be recovered and reused, and belongs to the field of composition of polymer chemicals and polymer compounds in polymers.

technical background

The industrial chain consisting of 1, 4-butanediol and tetrahydrofuran and its downstream products is one of the industries with global production capacity, production growth, technology renewal, market expansion and fastest development in the past decade. The driving force behind the development of this industry chain is the rapid increase in demand for the end products of the industry chain, and polytetramethylene ether glycol (PTMEG) is an important intermediate.

The early tetrahydrofuran polymerization process mostly uses liquid strong protonic acid. The commercially available liquid protonic acid as the initiator mainly includes perchloric acid process and fluorosulfonic acid process. US Du Pont, Quaker Oats, Peen, and Japan's Hodogaya have used or are still using PTMEG to produce PTMEG. The liquid strong proton acid process has obvious defects, the catalyst can not be recycled and reused, equipment corrosion caused by hydrolysis and water washing, separation difficult, acid and salty wastewater treatment. In order to solve the above problems, various processes such as fluorosulfonic acid resin, heteropoly acid, and natural clay catalyst have been successively developed.

In 1978, Du Pont of the United States developed a new process based on the original fluorosulfonic acid process, using a perfluorosulfonic acid resin catalyst as a catalyst for the polymerization of tetrahydrofuran. The catalyst partially swells and dissolves in the reaction medium, and the life of the catalyst is only 1 to 2 years. Under the reaction conditions, the catalyst is deactivated. In 1987, Asahi Kasei Corporation of Japan established the first industrial production unit using a heteropoly acid process of 2000t/a. The conversion rate of this process of tetrahydrofuran in a single cycle is very low, so industrial plants built are rare.

Therefore, a tetrahydrofuran polymerization catalyst with high development stability, long life, low cost, and higher single-cycle conversion rate is imminent.

Summary of the invention

The object of the present invention is to obtain a high-performance, low-cost tetrahydrofuran polymerization catalyst system by processing a perfluorosulfonic acid resin, thereby reducing the production cost of PTMEG and increasing the conversion rate.

Some perfluorosulfonic acid resins produced by the prior art may partially dissolve in tetrahydrofuran, resulting in difficulty in separation of the catalyst and the product, and may not be used as a catalyst for ring-opening polymerization of tetrahydrofuran; some may remain in the original form during the polymerization of tetrahydrofuran. However, in the case of stirring, the original particle form cannot be maintained, and the catalyst which is broken into powder form also increases the difficulty in separating the catalyst from the product at the end of the reaction. Generally, the separation of the catalyst and the product is carried out by a type of filtration through a metal filter, and the metal filter can only filter particles having a particle size exceeding a certain value, and the powdered catalyst may clog the filter or be introduced into the product through the filter. In, affect the purity of the product. Although some perfluorosulfonic acid resins can be used directly as four The hydrogen furan polymerization catalyst was used, but the catalytic effect was very weak. According to Comparative Examples 1, 2, the yield was less than 5%, and there was no industrial application value. Therefore, it is necessary to treat the perfluorosulfonic acid resin to obtain a high-performance, low-cost tetrahydrofuran polymerization catalyst system.

In order to solve the above technical problem, the technical solution adopted by the present invention is as follows:

(1) A catalytic system for catalyzing ring-opening polymerization of tetrahydrofuran, comprising a perfluorosulfonic acid resin, wherein the chemical formula of the perfluorosulfonic acid resin is:

■CF CF CFCF

y

OCF ₂ CF thousand O- -CF, ■S0 ₉ R

CF, where x=4~12; y=l; z=0,l,2; n=0~5; R=F, ONa, OH;

The perfluorosulfonic acid resin contains 10 to 30% of a separable material. The content of the separable material has an upper limit range of the lower limit and the lower limit. The upper limit of the content of the separable substance is 18 to 35%, and in this range, it may be less than 32%, and the optimum value is 30%. The lower limit of the content of the separable substance is in the range of 1 to 15%, and in this range, it may be higher than 8%, and the optimum value is 10%. Preferably, the perfluorosulfonic acid resin contains 10.70 to 29.16% of a separable material.

(2) The catalytic system according to (1), wherein the perfluorosulfonic acid resin has a particle diameter of 0.4 to 5.2 mm. The particle size of the perfluorosulfonic acid resin has an upper limit range of the lower limit and the lower limit. The upper limit of the particle size of the perfluorosulfonic acid resin is in the range of 1.0 to 6.4 mm, and may be less than 1.5 mm in this range, and the optimum value is 1.2 mm. The lower limit of the particle diameter of the perfluorosulfonic acid resin is 0.2 to 1.0 mm, and may be higher than 0.5 mm in this range, and the optimum value is 0.8 mm. Preferably, the perfluorosulfonic acid resin has a particle diameter of 0.8 to 1.2 mm. Among them, the particle size is the largest single axis size of the particles.

(3) The catalytic system according to any one of (1) to (2) wherein the perfluorosulfonic acid resin has a mass percentage of carbon elements of less than 20%. Preferably, the perfluorosulfonic acid resin has a mass percentage of carbon elements of less than 19%.

(4) The catalytic system according to any one of (1) to (3) wherein the perfluorosulfonic acid resin has a sulfur element content of less than 5% by mass.

(5) The catalytic system according to any one of (1) to (4) wherein the total mass percentage of the four elements C, H, 0, and F in the perfluorosulfonic acid resin is more than 92%.

(6) The catalytic system according to any one of (1) to (5) wherein the perfluorosulfonic acid resin has an ion exchange capacity ranging from 0.74 to 1.50. The ion exchange capacity has an upper limit range, that is, a lower limit range. The upper limit of the ion exchange capacity ranges from 1.2 to 2.0, and can be less than 1.8 in this range, and the optimum value is 1.15. The lower limit of the ion exchange capacity is in the range of 0.5 to 1.0, and can be higher than 0.6 in this range, and the optimum value is 0.8. Preferably, the ion exchange of the perfluorosulfonic acid resin The capacity ranges from 0.8 to 1.15.

(7) The catalytic system according to any one of (1) to (6) wherein the perfluorosulfonic acid resin has a specific surface area of less than 20 m ² /g.

(8) The catalytic system according to any one of (1) to (7) wherein the perfluorosulfonic acid resin does not contain a benzene ring structure.

(9) The catalytic system according to any one of (1) to (8) wherein the perfluorosulfonic acid resin has a weight loss of less than 30% between 0 and 350 °C.

(10) The catalytic system according to any one of (1) to (9) wherein the perfluorosulfonic acid resin is less than 50% at 350 to 600 °C.

(11) The catalytic system according to any one of (1) to (10) wherein the perfluorosulfonic acid resin has a mass percentage of silicon element and aluminum element of less than 0.1%.

(12) The catalytic system according to any one of (1) to (11) wherein the perfluorosulfonic acid resin is insoluble or partially swollen in tetrahydrofuran.

(13) The catalytic system according to any one of (1) to (12) wherein the separable material in the perfluorosulfonic acid resin is incapable of being in tetrahydrofuran, acetone, isopropanol, nitromethylpyrrolidone, dichloromethane Completely dissolved in toluene, benzene or a mixed solvent thereof.

(14) The catalytic system according to any one of (1) to (13), wherein the separable material is a separable material separated by dry or dry extraction with an organic solvent extraction.

(15) The catalytic system according to any one of (1) to (14), wherein the drying treatment comprises a nitrogen purge, a normal pressure drying, a reduced pressure drying, a moisture absorption drying, and/and a freeze drying.

(16) The catalytic system according to any one of (1) to (15), wherein the organic solvent extraction treatment comprises using tetrahydrofuran, 1,4-dioxane, methanol, ethanol, isopropanol, toluene, The benzene, N-methylpyrrolidone, and a mixed solvent thereof are subjected to extraction extraction treatment.

(17) A method of (1) - (16), wherein the method of the perfluorosulfonic acid resin comprises one or more of the following steps: granulation treatment, drying treatment, organic solvent extraction treatment.

(18) The method according to (17), wherein the granulation treatment comprises a melt extrusion or a low temperature freeze pulverization treatment.

(19) The method according to (17), wherein the drying treatment comprises nitrogen purge, atmospheric drying, reduced pressure drying, moisture drying or/and freeze drying.

(20) The method according to any one of (17) to (19), wherein the granulation treatment comprises a pulverization treatment by melt extrusion or low temperature freezing.

(21) The method according to any one of (17) to (20), wherein the perfluorosulfonic acid resin and the organic solvent are mixed at a volume ratio of 1:1 to 1:30. The ratio of the perfluorosulfonic acid resin to the organic solvent has an upper limit range of the lower limit and the lower limit. The upper limit of the volume ratio of the perfluorosulfonic acid resin to the organic solvent is 1:10 to 1:36, and may be less than 30 in this range. The best value is 18. The lower limit of the volume ratio of the perfluorosulfonic acid resin to the organic solvent is 1:1 to 1:15, and in this range, it may be higher than 1:5, and the optimum value is 1:12.

(22) The method according to any one of (17) to (21), wherein the organic solvent comprises tetrahydrofuran, 1,4-dioxane, methanol, ethanol, isopropanol, toluene, benzene, N-A Pyrrolidone, and a mixed solvent thereof.

(23) The method according to any one of (17) to (22), wherein the extracting and extracting step is carried out at a temperature of 50 to 130 ° C and a pressure of 51 to 200 kPa. The extraction extraction temperature has an upper limit range of the lower and lower limits. The upper limit of the extraction temperature is in the range of 100 to 160 ° C, and may be lower than 150 ° C in this range, and the optimum value is 120 ° C. The lower limit of the extraction temperature is 30 to 80 ° C, and in this range, it can be higher than 40 ° C, and the optimum value is 60 ° C. The extraction extraction pressure has an upper limit range of the lower and lower limits. The upper limit of the extraction pressure is from 100 to 220 kPa, and in this range, it can be less than 200 kPa, and the optimum value is 180 kPa. The lower limit of the extraction pressure is 50 to 85 kPa, and in this range, it can be higher than 60 kPa, and the optimum value is 80 kPa.

(24) The method according to any one of (17) to (23) wherein the drying step is carried out at 100 to 150 ° C under a vacuum of 0.3 to 14 kPa, and the drying time is 6 to 12 hours. The drying temperature has an upper limit range of the lower and lower limits. The upper limit of the drying temperature ranges from 80 to 160 ° C, and can be lowered by 150 ° C in this range, and the optimum value is 130 ° C. The lower limit of the drying temperature is 60 to 120 ° C, and in this range, it can be higher than 100 ° C, and the optimum value is 110 ° C. The dry vacuum has an upper limit range of the lower and lower limits. The upper limit of the dry vacuum is 12 to 40 kPa, and in this range, it may be lower than 24 kPa, and the optimum value is 12 kPa. The lower limit of the dry vacuum is in the range of 0.1 to 10 kPa, and can be higher than 1 kPa in this range, and the optimum value is 8 kPa. The drying time has an upper limit range of the lower and lower limits. The upper limit of the drying time is 10 to 20 hours, and in this range, it can be lower than 16, and the optimum value is 12 hours. The lower limit of the drying time is 4~10h, which can be higher than 6h in this range, and the best value is 8h.

(25) A catalytic system for catalyzing ring-opening polymerization of tetrahydrofuran, which is obtained by the method described in any one of (17) to (23).

(26) The catalytic system according to (25), wherein the mass percentage of the carbon element in the catalytic system is greater than 20%.

(27) The catalytic system according to any one of (25) to (26) wherein the mass percentage of sulfur element in the catalytic system is less than

5%.

(28) The catalytic system according to any one of (25) to (27), wherein the total mass percentage of the four elements C, H, 0, and F in the catalytic system is greater than 92%.

(29) The catalytic system according to any one of (25) to (28), wherein the catalytic system has an ion exchange capacity ranging from 0.8 to 0.9.

(30) The catalytic system according to any one of (25) to (29), wherein the catalytic system has a specific surface area of less than 20 m ² /g.

(31) The catalytic system according to any one of (25) to (30) wherein the catalytic system has a particle diameter of 0.8 to 1.2 mm. (32) The catalytic system according to any one of (25), wherein the content of the silicon element and the aluminum element in the catalytic system is less than 0.1%.

(33) The catalytic system according to any one of (25), wherein the catalytic system does not contain a benzene ring structure.

(34) The catalytic system according to any one of (25), wherein the catalyst system has a weight loss of less than 25% between 0 and 350 °C.

(35) The catalytic system according to any one of (25), wherein the catalyst system has a weight loss of more than 50% between 350 and 600 °C.

(36) The catalytic system according to any one of (25), wherein the catalytic system is used as a catalytic conversion of tetrahydrofuran in a ring-opening polymerization of more than 20%.

(37) The catalytic system according to any one of (25), wherein the catalytic system has a number average molecular weight of 400 to 20000 g/mol as a product of catalytic ring-opening polymerization of tetrahydrofuran. The number average molecular weight of the product has an upper limit range, that is, a lower limit range. The product number average molecular weight in the range of the upper limit 2000~24000 g / mol, in this range may be less than 10000 g / mol, the optimum value of 4000 g / mol ₀ the lower limit of the range of the product number average molecular weight of 200~1800 g /mol, in this range can be higher than 500 g / mol, the best value is 650 g / mol. Preferably the number, the product average molecular weight ranging 2215~3596 g / mol ₀

Table 1 Analytical characterization results of untreated perfluorosulfonic acid resin

Analysis Example 1 Inventive Example 2 Inventive Example 3 Inventive Example 4 Inventive Example 5 Inventive Example 6 Comparative Example No.

Method Resin 1 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 7

C: 16.15 18.66 15.26 17.92 17.44 16.36 34.59 Elemental analysis

1 H: 1.85 1.36 2.39 0.96 0.86 1.10 6.06 wt%

N: 0.09 0.08 0.14 0.09 0.08 0.07 0.08

C, H, F, C, H, F, C, H, F, C, H, F, C, H, F, C, H, F, C, H, F,

0 Total 0 Total 0 Total 0 Total 0 Total 0 Total 0 Total 里 : Lane: Lane: Lane: Lane: Lane: Lane:

99.1% 98.1% 98.8% 99.3% 99.1% 98.8% 91.8%

S: S: S:

S: 1.93% S: 1.05% S: 1.06% S: 8.22%

0.855% 0.699% 0.737%

XRF semi-fixed K: K: K: K:

2 Fe: Fe: Ah amount analysis 0.00248 0.00340 0.00101 0.00509

0.00374% 0.00191% 0.0115%

% % % %

Fe: Fe: Fe: Fe: Fe:

0.00262% None 0.00210% 0.00194% 0.00278% None 0.00334% No silicon aluminum, such as silicon aluminum, no silicon aluminum, no silicon aluminum, no silicon aluminum, silicon aluminum, etc.

Si: Other elements such as other elements; other elements such as other elements;

0.00765%

BET ratio table

3 1 m ² /g 1 m ² /g 1 m ² /g 2m ² /g 1 m ² /g 2m ² /g 21 m ² /g Area Main particle size

Distributed in

Particle size Main particle size Main particle size Main particle size Main particle size Main particle size 1.0-1.5

Distribution in distribution in distribution in distribution in particle size analysis mm,

2 - 3 mm 3 - 4 mm 4 - 5 mm 3 - 4 mm 3 - 4 mm 0.2 - 0.4 Average particle size

Inside the inner inner mm

1.2mm ;

Water content: wave water content: wave water content: wave water content: wave water content: wave water content: wave water content: wave number number number number number

3418.8 3419.2 3418.7 3418.9 3468.3 3450.8 3408.8

1638.7; 1638.9; 1638.8; 1643.3; 1639.1; 1638.5; 1704.9; present and present day

CF2&CF: CF2&CF: CF2&CF: CF2&CF: CF2&CF: CF2&CF: Wave number Wave number Wave number Wave number Wave number Wave number

Benzene containing ring and infrared analysis 1213.0 1213.4 1212.7 1212.8 1210.9 1219.1

Sulfonic acid group:

1152.6 ; 1152.8 ; 1152.5 ; 1153.1 ; 1151.9 ; 1151.5 ;

Wave number, sulfonic acid, sulfonic acid, sulfonic acid, sulfonic acid, sulfonic acid

1133.0 Base: Wave number Base: Wave number Base: Wave number Base: Wave number Base: Wave number Base: Wave number

1026.7 1060.0; 1059.0; 1058.6; 1057.0; 1058.2; 1059.5;

833.0 Ether-containing bond: Ether-containing bond: Ether-containing bond: Ether-containing bond: Ether-containing bond: Ether-containing bond: Wave number Wave number Wave number Wave number Wave number Wave number

980.0 978.1 977.8 977.3 977.4 978.2

Catalyst containing catalyst containing catalyst containing catalyst containing catalyst containing catalyst containing catalyst

Water (and low water (and low water (and low water (and low water (and low water (and low water (and low)

Boiling point, boiling point, boiling point, boiling point, boiling point, boiling point, boiling point, boiling point, boiling point, melting point

Agent) agent) agent) 10%, 8%, agent) 15%,

10.2%, 6.2%, 10.4%, 29.7%, divided into three segments, three segments, three segments, three segments

Three segments lost three segments lost three segments lost two segments lost weight, warming heavy, warming heavy, warming

Thermogravimetric analysis Heavy, warming heavy, warming heavy, warming heavy, heating up to 280 degrees to 280 degrees to 270 degrees

(TGA, from 300 degrees to 289 degrees to 281 degrees to 277 degrees weight loss weight loss weight loss

Heating rate, weightlessness, weightlessness, weightlessness, weightlessness

2.3%, 2.8%, 3.3%,

Is 10 degrees / 6.4%, 3.5%, 5.6%, 1.0%,

280~375 280~380 270~370

Minutes, nitrogen 300~375 289~392 28b 367 277~348 degree weight loss weight loss weight loss

Gas environment) loss of weight, weight loss, weight loss, weight loss

1.1%, 8.0%, 5.8%,

14.4%, 4.2%, 2.2%, 31.8%, 375 degrees at 380 degrees to 375 degrees

375 degrees at 392 degrees to 367 degrees at 348 degrees, then lose weight, lose weight, and lose weight

After losing weight, weight loss, weight loss, weight loss, 78.5%, 80.0%, 74.0%,

66.4%, 86.1%, 79.8%, 4.8%, the last remaining residue, the last remaining, the last remaining

The last residue is the last residue and the last residue is 2%. The amount is 2%. The amount is 1.8%.

The amount is 2%. The amount is 2%. The amount is 2%. 32.7%. In THF

Solubility test

Test (sample catalyst and catalyst and catalyst and catalyst and catalyst and catalyst and catalyst part mouth straight undissolved undissolved undissolved undissolved undissolved undissolved dissolved THF solution

24h) Ion exchange

8 0.9 0.9 0.95 0.80 0.90 1.15

Capacity

Table 2 Comparison of properties of perfluorosulfonic acid resin before and after treatment

X-ray fluorescence spectroscopy before and after treatment, elemental analysis, infrared TGA

(X F) amount change catalyst water

(and low boiling point

Agent) 10%, points

C, H, F, 0 total water content: wave number 3418.8, 1638.7; three sections weight loss, liter

C: 16.15 Quantity: 99.1%; S: Contains CF2&CF: Wavenumber 1213.0, temperature is 280 degrees missing

H 1.3 0.855%; K: 1152.6; sulfonic acid group: wave number weight 2.3%, before

N: 0.09 0.00248%; Fe: 1060.0; 280~375 degrees lost

0.00262% ; etheric bond: wave number 980.0; weight 7.7%, 375

Tree

Weight loss after m degree, mass reduction

78.5%, last disability 29.16%

1

The balance is 2%.

Warm up to 270 degrees

C, H, F, 0 total

Weight loss 5.9%,

Amount: 98.6%; S: Contains CF2&CF: wave number 1209.2,

Extraction C: 21.22 270~390 degrees lost

1.35%; Fe: 1152.0; sulfonic acid group: wave number

Drying H: 1.04 weighs 9.5%, 390

0.00340%; K: 1056.6;

After N: weight loss after 0.04 degrees

0.00525%; Si: ether-containing bond: wave number 981.9;

81.3%, last disability

0.0137%

The balance is 3.3%.

Catalyst containing water

(and low boiling point

Agent) 8%, divided into three

C, H, F, 0 total water content: wave number 3419.2, segment weight loss, temperature rise

Tree C: 18.66 Quantity: 98.1%; S: 1638.9; Contains CF2&CF: Wavenumber to 280 degrees weight loss

m Pre-quality reduction

H: 1.36 1.93%; Fe: 1213.4, 1152.8; sulfonic acid group: 2.8%, 280~ 20.0%

2 N: 0.08 0.00374%; K: wave number 1059.0; 380 degree weight loss

0.00101%; etheric bond: wave number 978.1; 8.0%, 380 degrees

Weight loss in the future

79.0%, last disability

The remaining amount is 3%. Warm up to 270 degrees

C, H, F, 0 total weight loss 5.7%,

Contains CF2&CF: wave number 1209.4,

Extraction amount: 98.5%; S: 270~390 degrees loss

1151.7; sulfonic acid group: wave number

Drying 1.45%; Fe: weighing 10.3%, 390

1056.6;

After 0.00574%; K: weight loss after

With ether bond: wave number 981.9;

0.00678%; 80.2%, last disability

The balance is 3.8%.

Catalyst containing water

(and low boiling point

Qi 10.2%, points

C, H, F, 0 total water content: wave number 3418.9, 1643.3; three sections weight loss, liter

C: 17.92 Amount: 99.3%; S: Contains CF2&CF: Wavenumber 1212.8, temperature up to 300 degrees

H: 0.96 0.699%; K: 1153.1; weighs 6.4%, before

N: 0.09 0.00101%; Fe: sulfonic acid group: wave number 1057.0; 300~375 degree loss

0.00194%; etheric bond: wave number 977.3; weight 14.4%, 375

Weight loss after

65.1%, last disability

After drying, the mass balance is 3.3%.

Reduce the tree temperature to 280 degrees

18.08%; m weight loss 6.4%,

Contains CF2&CF: wave number 1206.8, after extraction and drying

4 C: 20.87 C, H, F, 0 total 280~380 degrees loss

Dry 1151.5; Sulfonic acid group: Wave number Mass reduction H: 0.56 Amount: 98.7%; S: Weight 7.8%, 380 after 1058.6; 18.09%; N: 0.08 1.30%; Weight loss after degree

Containing ether bond: wave number 976.5;

83.5%, last disability

The balance is 2.3%.

Warm up to 260 degrees

C, H, F, 0 total weight loss 4.4%,

Contains CF2&CF: wave number 1206.5,

Extraction C: 21.31 Quantity: 98.5%; S: 260~380 degrees loss

1152.4; sulfonic acid group: wave number

Drying H: 1.00 1.48%; Fe: 8% by weight, 380 degrees

1057.3;

After N: 0.10 0.00650%; Ca: weight loss later

Containing ether bond: wave number 983.3;

0.00297%; 84.7%, last disability

The balance is 2.9%.

Catalyst containing water

(and low boiling point

6.2%, points

Quality after drying

C, H, F, 0 total water content: wave number 3468.3, 1639.1; three-stage weight loss, liter

Decrease tree C: 17.44 Quantity: 99.1%; S: Contains CF2&CF: wave number 1210.9, temperature up to 289 degrees

Pre-position 10.7%; m H: 0.86 0.737%; K: 1151.9; weight 3.5%,

Before extraction, after drying

5 N: 0.08 0.00509%; Fe: sulfonic acid group: wave number 1058.2; 289~392 degrees loss

Mass reduction 0.00278%; ether-containing bond: wave number 977.4; weight 4.2%, 392

10.93%; weight loss after the degree

86.1%, last disability

The balance is 2%. Warm up to 280 degrees

Weight loss 4.5%,

Contains CF2&CF: wave number 1207.1,

C: 20.79 C, H, F, 0 total 280~380 degrees loss Drying 1150.3; containing sulfonic acid group: wave number

Η: 0.40 quantity: 98.6 %; S: weight 5.2 %, 380 after 1063.5;

Ν: 0.10 1.39 %; weight loss after the degree

With ether bond: wave number 979.0;

86.2%, last disabled

The remaining amount is 4.1%.

C, H, F, 0 total temperature rises to 280 degrees

Amount: 97.8 % ; S: weight loss 3.5 %,

Contains CF2&CF: wave number 1209.1,

Extraction C: 22.30 1.81%; Fe: 280~390 degrees lost

1152.1; sulfonic acid group: wave number

Dry Η: 0.78 0.00710%; K: weighs 4.2 %, 390

1061.3;

After Ν: 0.09 0.0141 %; Si: weight loss after degree

Containing ether bond: wave number 981.8;

0.0116%; Ah 88.0%, last disability

0.0151%; balance 4.3%.

Table 3 Untreated perfluorosulfonic acid resin as catalyst polymerization result

According to the results in Table 1, the sample resin 7 was partially dissolved in tetrahydrofuran, resulting in difficulty in separation of the catalyst from the product. Although it has a certain catalytic effect on the ring-opening polymerization of tetrahydrofuran, the catalyst which is dissolved after the completion of the polymerization is difficult to separate from the polymerization product, and thus is not recommended for industrial production. According to the results in Table 3, although the sample resins 1 to 6 were maintained in the original form during the polymerization of tetrahydrofuran without stirring, the sample resin 3 and the resin 6 sample particles could not maintain the original form with stirring. The catalyst that is broken into powder also increases the difficulty of separating the catalyst from the product at the end of the reaction. Generally, the separation of the catalyst and the product is carried out by a type of filtration through a metal filter, and the metal filter can only filter particles having a particle size exceeding a certain value, and the catalyst which becomes a powder may block the filter or be carried into the product through the filter. In, affect the purity of the product. Therefore, the sample resin 3 and the resin 6 cannot be used as a tetrahydrofuran polymerization catalyst.

I. The ion exchange capacity of the other samples is less than or equal to 0.9. Since the ion exchange capacity is obtained by preparing perfluorosulfonate The content of the perfluorosulfonyl ether comonomer in the acid resin is determined, and the content of tetrafluoroethylene in the comon determines the structural stability of the final perfluorosulfonic acid resin product. The content of the two monomers is oppositely changed, that is, the higher the content of the perfluorosulfonyl ether comonomer, the higher the ion exchange capacity, and the lower the content of the tetrafluoroethylene comonomer, resulting in perfluorosulfonic acid The lower the structural stability of the resin. I. The ion exchange capacity of the perfluorosulfonic acid resin having an optimum catalytic stability is in the range of 0.9 or less. However, the catalytic activity of the catalyst is determined by the ion exchange capacity. According to the normal thinking, when the catalyst is selected, a product having a high catalytic activity should be selected as the catalyst, but here, a product having a low ion exchange capacity and low catalytic property is selected. 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。.

The perfluorosulfonic acid resin of the present invention, if used directly as a catalyst for polymerization of tetrahydrofuran, has a weak catalytic effect. According to Comparative Examples 1, 2, the yield is less than 5%, and there is no industrial application value. As shown in Table 1, the physicochemical properties of various perfluorosulfonic acid resins are shown by infrared analysis. The resin contains sulfonic acid groups, fluorocarbon ether bonds, and a large amount of water. From the TGA analysis, the prepared perfluorosulfonic acid resin contains A large amount of water and other separable materials. If the direct use not only affects the conversion of tetrahydrofuran polymerization, but also contains a large amount of impurities in the polytetrahydrofuran product, it is necessary to pretreat the perfluorosulfonic acid resin to have the application value of catalyzing the polymerization of tetrahydrofuran. Extraction with an organic solvent is extracted for a sufficient period of time to allow the separable material to be extracted, and the content of the separable material is removed in the range of 10 to 30%, wherein the content of the separable material in most of the resin samples ranges from 10 to 27 %. The results in Table 2 show the difference in physicochemical properties before and after resin treatment. From the elemental analysis results, the carbon content of the catalytic system is greatly increased, exceeding 20%. The content of S element can represent the size of ion exchange capacity, and the content of S element in X-ray fluorescence spectrum is obviously improved, indicating that the pretreatment can not only improve the catalytic activity by removing low molecular weight impurities, but also improve the ion exchange capacity. Catalytic activity. It can be seen from the comparison before and after the infrared spectrum analysis that the treated catalyst system does not contain water, and the other structures are unchanged. According to the TGA results, the thermal stability of the perfluorosulfonic acid resin after pretreatment is also improved, and the sample does not contain low boiling components. The treated perfluorosulfonic acid resin is used as a tetrahydrofuran polymerization catalyst to achieve the purpose of catalyzing the polymerization of tetrahydrofuran, and the conversion of tetrahydrofuran is high, and the polytetrahydrofuran product is not affected by impurities in the resin. It is worth mentioning that the prior art perfluorosulfonic acid resin generally has a large particle size, and the average particle diameter is more than 2 mm and the maximum is 5 mm, but as a catalyst, the specific surface area is too small. The perfluorosulfonic acid resin is a solid polymer particle which can be increased in specific surface area by changing the particle size. The granules having a particle size of 0. 8~1. 2mm are obtained by the method of the granules having a particle size of 0. 8~1. . Table 4 compares the catalytic effects of the catalytic system

According to the results in Table 2, the mass reduction before and after the resin treatment was remarkable, and the obtained perfluorosulfonic acid resin contained a considerable amount of separable matter, which would affect the effect of use as a catalyst for the polymerization of tetrahydrofuran. It can be seen from Table 4 that when the resin directly catalyzes the polymerization of tetrahydrofuran, the catalytic yield is less than 5%, and the catalytic effect is not good; and the catalytic system obtained by the treatment of the catalyst catalyzes the polymerization yield of tetrahydrofuran to exceed 20%, and can be applied to industrial applications. In production, it has practical value. It is worth mentioning that the catalytic activity of the perfluorosulfonic acid resin obtained by drying and extraction drying is high, but the effect of drying and extraction of perfluorosulfonic acid resin is better than that of drying only. The performance is relatively stable.

The catalytic system for catalytic ring-opening polymerization of tetrahydrofuran provided by the invention can overcome the obvious defects of the liquid protonic acid process, so that the catalyst can be recycled and reused, the corrosion of equipment caused by hydrolysis and washing process can be avoided, and the separation is avoided. , Reduce the treatment of acid and salty wastewater, etc. The catalytic system has good stability and long service life, and the single cycle conversion rate is high when catalyzing the polymerization of tetrahydrofuran, and the production cost of the catalytic system can be further reduced. detailed description

Example 1

Preparation of catalytic system:

Using tetrafluoroethylene and a vinyl monomer bearing a sulfonyl fluoride group, at 1, V, 131.2 kpa, 1, 1, 2 - trichloro-1, 2, 2-trifluoroethane The solvent, using azobisisobutyronitrile as an initiator, initiates radical copolymerization of the two monomers to obtain a fluoropolymer containing a sulfonyl fluoride group. The polymer containing a sulfonyl fluoride group is alkalized with a sodium hydroxide solution to obtain a polymerization containing a sodium sulfonate group, which is then treated with sulfuric acid to obtain a perfluorosulfonic acid resin 1 to 6. Resin 7 is a benzenesulfonic acid resin. Resin 1 was directly used as the catalytic system 1, and resin 7 was directly used as the catalytic system 2.

The perfluorosulfonic acid resins 4, 5, 1, and 2 were treated by the following methods to obtain sulfonic acid group-containing fluoropolymer catalytic systems 3, 4, 5, and 6 respectively:

The granules having a particle size of 0. 8~1. 2mm or so;

B. The perfluorosulfonic acid resin having a particle diameter of about 0.8 to 1.2 mm is mixed with an organic solvent such as tetrahydrofuran in a ratio of from 1/1 to 1/30;

C. The temperature is controlled at 50~130 ° C, and the pressure is extracted from 51 to 200 kPa, and the extraction is sufficient for the low molecular weight impurities in the resin to be sufficiently extracted, and the mass of the soluble component is about 10% to 30% of the total mass;

D. The treated perfluorosulfonic acid resin product in c is dried at a temperature of from 100 to 150 ° C under a vacuum of 0.3 to 14 kPa for a sufficiently long period of time, generally 6 to 12 hours, to further remove low molecular weight impurities;

E. Recovery of the treated perfluorosulfonic acid resin described in d).

The perfluorosulfonic acid resins 4, 5, and 1 are treated by the following methods to obtain sulfonic acid group-containing fluoropolymer catalytic systems 7, 8, 9:

The granules having a particle size of 0. 8~1. 2mm or so;

B. The treated perfluorosulfonic acid resin product in A is dried at a temperature of 100 to 150 ° C and a vacuum of 0.3 to 14 kPa for a sufficiently long period of time, generally 6 to 12 hours, to further remove low molecular weight impurities;

C. Recovery of the treated perfluorosulfonic acid resin described in B.

Chicken Case 2:

Polymerization using the catalytic system 5 of this patent:

In a 500 mL three-necked magnetic flask, the three-necked flask was connected to a spherical water condenser, a constant pressure dropping funnel, and a thermometer. 20 g of the catalytic system 5 of the invention was added. To the catalytic system, 350 mL of tetrahydrofuran dried with calcium hydride was added, and 7 g of propionic anhydride was added dropwise to the three-necked vial with a constant pressure dropping funnel. The polymerization was carried out at 55 ° C and the reaction was stirred for 12 h. The product was a brownish yellow liquid with a polymerization yield of 35%. Example 3:

Polymerization using the catalytic system 6 of this patent:

In a 500 mL three-necked magnetic flask, the three-necked flask was connected to a spherical water condenser, a constant pressure dropping funnel, and a thermometer. 20 g of the catalytic system 6 of the present invention was added. To the catalytic system, 350 mL of tetrahydrofuran dried with calcium hydride was added, and 7 g of acetic anhydride was added dropwise to the three-necked vial using a constant pressure dropping funnel. The polymerization was carried out at 55 ° C and the reaction was stirred for 12 h. The product was a brownish yellow liquid with a yield of 28%.

Difficulties 4:

Polymerization using the catalytic system 7 of this patent:

In a 500 mL three-necked magnetic flask, the three-necked flask was connected to a spherical water condenser, a constant pressure dropping funnel, and a thermometer. 20 g of the catalytic system 7 of the present invention was added. To the catalytic system, 350 mL of tetrahydrofuran dried with calcium hydride was added, and 7 g of propionic anhydride was added dropwise to the three-necked vial using a constant pressure dropping funnel. The polymerization was carried out at 55 ° C and the reaction was stirred for 12 h. The product was a brownish yellow liquid with a polymerization yield of 30%.

Example 5 (Comparative Example 1):

Continuous polymerization using Resin 1 in this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and it was stable after 3 hours, and the yield was 3.5%.

e (Comparative 2):

Continuous polymerization using Resin 7 in this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and it was stable after 2 h, and the yield was 4.2%.

Chicken Case 7:

Continuous polymerization using the catalytic system 1 of this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and the stability was achieved after 5 h, the yield was 28.7%, the number average molecular weight of the polymer was 2215, and the molecular weight distribution was 2.14. Example 8

Continuous polymerization using the catalytic system 2 of this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and the stability was achieved after 5 h, and the yield was 22%.

Difficulty 9:

Continuous polymerization using the catalytic system 2 of this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and the stability was achieved after 7 h, the yield was 22.9%, the number average molecular weight of the polymer was 2,275, and the molecular weight distribution was 2.49.

Example 10

Continuous polymerization using the catalytic system 3 of this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and the stability was achieved after 7 h, the yield was 28.9%, the number average molecular weight of the polymer was 2267, and the molecular weight distribution was 2.04.

Example 11:

Continuous polymerization using the catalytic system 4 of this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and it was stable after 6 hours, the yield was 27.3%, the number average molecular weight of the polymer was 2475, and the molecular weight distribution was 2.07.

Chicken Case 12:

Continuous polymerization using the catalytic system 5 of this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and it was stable after 8 hours, the yield was 27.4%, the number average molecular weight of the polymer was 2,248, and the molecular weight distribution was 2.23. Example 13 _:

Continuous polymerization using the catalytic system 6 of this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and the stability was achieved after 5 hours, the yield was 21.1%, the number average molecular weight of the polymer was 3596, and the molecular weight distribution was 1.66.

Difficulty 14 _:

Continuous polymerization using the catalytic system 7 of this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and it was stable after 5 h, and the yield was 30.9%.

Money example 15:

Continuous polymerization using the catalytic system 7 of this patent:

In a 1 L reactor with mechanical stirring, 57.36 g of the catalytic system of the invention was added. 750 mL of tetrahydrofuran dried with calcium hydride was added to the catalyst system, and a solution of 2.7 wt% acetic acid and 2.6 wt% acetic anhydride in tetrahydrofuran was added to the reactor at a flow rate of 12 mL/min while the reactor was fed at equal speed. The product solution flows out. The polymerization temperature was 50 ° C, and it was stable after 5 hours, the yield was 30.4%, the number average molecular weight of the polymer was 2,703, and the molecular weight distribution was 2.01.

The above embodiments are not exhaustive of the specific embodiments, and other embodiments may be made. The above embodiments are intended to illustrate the present invention, and do not limit the scope of the present invention. All applications that are simply changed by the present invention fall within the scope of the present invention. Within the scope of protection of the invention.

This patent specification uses examples to illustrate the invention, including the best mode, and the invention may be made and used by those skilled in the art. The scope of the invention is intended to be included within the scope of the claims and the specific embodiments and These other examples are also intended to fall within the scope of the claims of the invention, as long as they contain the technical features described in the same written language, or they contain the technical features described in a similar literal language that is not substantially different from the claims.

The entire contents of all patents, patent applications and other references are hereby incorporated by reference. However, if a term in this application conflicts with a term already included in the reference, the terminology of the present application is preferred.

All ranges disclosed herein are inclusive of the endpoints, and the endpoints are combined independently of each other. It should be noted that "first", "second" or similar words do not mean any order, quality or importance, but are used to distinguish different technical features. The modifier "about" used in conjunction with the quantity contains the value and content context specification

Claims

WO 2015/070606 Claim PCT/CN2014/080215

A catalytic system for catalyzing ring-opening polymerization of tetrahydrofuran, comprising a perfluorosulfonic acid resin, characterized in that: the chemical formula of the perfluorosulfonic acid resin is:

Where x=4~12; y=l; z=0,l,2; n=0~5; R=F, ONa, OH;

The perfluorosulfonic acid resin contains 10 30% of a separable material.

The particle size of the perfluorosulfonic acid resin is 0.44 5. 2

The catalytic system according to claim 1 or 2, wherein the perfluorosulfonic acid resin has one or more of the following properties: a mass percentage of carbon element is less than 20%, and a mass of sulfur element Percentage less than 5% CH 0 F The total mass percentage of the four elements is greater than 92%, and the ion exchange capacity is in the range of 0.74 1. 50, and the specific surface area is less than 20 m ² /g.

The catalytic system according to any one of claims 1 to 3, wherein the perfluorosulfonic acid resin does not contain a benzene ring structure.

The catalytic system according to any one of claims 1 to 4, wherein the perfluorosulfonic acid resin loses less than 30% at 0 350 ° C.

The catalytic system according to any one of claims 1 to 5, wherein: the perfluorosulfonic acid resin is less than 50% at 350 600 °C

1%。 The perfluorosulfonic acid resin, the mass percentage of silicon and aluminum is less than 0.1%

The catalytic system according to any one of claims 1 to 7, wherein the perfluorosulfonic acid resin is insoluble or partially swollen in tetrahydrofuran.

The catalytic system according to any one of claims 1 to 8, wherein the separable material in the perfluorosulfonic acid resin is incapable of being in tetrahydrofuran, acetone, isopropanol, nitromethylpyrrolidone, dichloro Completely dissolved in methane, toluene, benzene or a mixed solvent thereof.

The catalytic system according to any one of claims 1 to 9, wherein the separable material is a separable material which is separated by drying or organic solvent extraction and drying.

The catalytic system according to any one of claims 1 to 10, wherein the drying treatment comprises nitrogen purging, atmospheric drying, reduced pressure drying, hygroscopic drying or/and freeze drying. WO 2015/070606 Claim PCT/CN2014/080215

The catalytic system according to any one of claims 1 to 11, characterized in that the organic solvent extraction and extraction treatment comprises using tetrahydrofuran, 1,4-dioxane, methanol, ethanol, isopropanol , toluene, benzene, N-methylpyrrolidone, and a mixed solvent thereof are subjected to extraction extraction treatment.

A method for treating a perfluorosulfonic acid resin according to any one of claims 1 to 12, which comprises one or more of the following steps: granulation treatment, drying treatment, organic solvent extraction and extraction deal with.

The method according to claim 13, wherein the drying treatment comprises nitrogen purge, atmospheric drying, reduced pressure drying, moisture absorption drying, and/and freeze drying.

The method according to claim 12 or 13, wherein the granulation treatment comprises a melt extrusion or a low temperature freeze pulverization treatment.

The method according to any one of claims 13 to 15, wherein the perfluorosulfonic acid resin and the organic solvent are mixed at a volume ratio of 1:1 to 1:30.

The method according to any one of claims 13 to 16, wherein the organic solvent comprises tetrahydrofuran, 1,4-dioxane, methanol, ethanol, isopropanol, toluene, benzene, N- Methyl pyrrolidone, and a mixed solvent thereof.

The method according to any one of claims 13-17, wherein: the extracting and extracting step is carried out at a temperature of 50 to 130 ° C and a pressure of 51 to 200 kPa, and the extraction extraction time is 6 ~36h.

The method according to any one of claims 13 to 18, wherein the drying step is carried out at 80 to 150 ° C, the degree of vacuum is 0.3 to 14 kPa, and the drying time is 6 to 12 hours.

A catalytic system for catalyzing ring-opening polymerization of tetrahydrofuran, characterized in that the catalytic system is obtained by the method according to any one of claims 13-19.

The catalytic system according to claim 20, wherein: the catalytic system has one or more of the following properties: a mass percentage of carbon element is greater than 20%, and a mass percentage of sulfur element is less than 5% The specific mass percentage of the four elements of C, H, 0, and F is greater than 92%, and the ion exchange capacity is in the range of 0. 8~0. 9, and the specific surface area is less than 20 m ² /g.

2〜1的让。 The catalyst system having a particle size of 0. 8~ 1. 2 let.

The mass percentage of the silicon element and the aluminum element in the catalytic system is less than 0.1%.

The catalytic system according to any one of claims 20 to 23, wherein the catalytic system does not contain a benzene ring structure.

The catalytic system according to any one of claims 20 to 24, wherein the catalytic system loses less than 25 % between 0 and 350 °C.

The catalytic system according to any one of claims 20 to 25, wherein the catalytic system is at 350~ WO 2015/070606 Claim PCT/CN2014/080215

The loss is greater than 50% between 600 °C.

The catalytic system according to any one of claims 20 to 26, wherein the catalytic system has a conversion ratio of more than 20% for catalytic ring-opening polymerization of tetrahydrofuran.

The catalytic system according to any one of claims 20 to 27, wherein the catalytic system has a number average molecular weight as a product of catalytic ring-opening polymerization of tetrahydrofuran in the range of 400 to 20,000 g/mol.