CN103524749B - A kind of polysiloxane-polyarylate segmented copolymer and Synthesis and applications - Google Patents

Abstract

The invention discloses a polysiloxane-polyarylate block copolymer as well as its preparation and application. Described polysiloxane-polyarylate block copolymer is shown in the following formula: . The surface of the block copolymer of the invention has low surface energy and strong hydrophobicity; it has an obvious microphase separation structure and has great application value in the field of blood compatibility materials. The preparation process is as follows: using fluorine-containing/fluorine-free olefin-terminated polyarylate and fluorine-containing/fluorine-free hydrogen-terminated polysiloxane as raw materials, using tetrahydrofuran, isopropanol, toluene and benzotrifluoride in One or more than two are solvents; under the action of catalyst 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) or chloroplatinic acid, hydrosilylation is added. The synthesis method is simple, the reaction conditions are mild and easy to control, and the industrial production is easy.

Description

A kind of polysiloxane-polyarylate block copolymer and its preparation and application

technical field

The invention relates to a polysiloxane-polyarylate block copolymer and its preparation and application, belonging to the technical field of block copolymers.

Background technique

Due to the existence of two or more monomer segments with different properties in multi-component polymers such as block copolymers, when the monomer segments are incompatible, phase separation tends to occur, forming a scale from nanometer to micron. This kind of phase separation is called microphase separation, and the structure formed by different phase regions is called microphase separation structure (Liu Honglai, Hu Ying, Chinese Journal of Chemical Engineering, 2003, 54:440-443). It is because of these heterogeneous structures that this kind of multi-component polymers has many excellent properties. Existing studies have shown that in the fields of blood compatibility materials, anti-fouling coatings and anti-icing coatings, polymer materials with microphase separation structures exhibit excellent performance, and various countries have carried out certain research on this , (Gui Taijiang, China Paint 2005, 20(10): 26-28; MajumdarP, W, Polymer, 2007, 48(26): 7499-7509; DongmeiYu, YunhuiZhao, HuiLi, HengzhiQi, BoLi, XiaoyanYuan, Progress in Organic Coatings76(2013 )1435–1444.)

Polyarylate refers to a polymer with aromatic rings connected to both ends of the ester group. It was first industrialized by Unitika Company in Japan in 1973. It has excellent properties such as high heat resistance and high heat distortion temperature, but it also has high melt viscosity, poor fluidity, and processing difficulties. In order to improve the processing performance of polyarylate and expand its application fields, researchers from various countries use blending. Polyarylate has been modified in many ways by means of copolymerization and filling, and various modified polyarylate materials with excellent performance have been obtained, which meet the needs of different fields. There are a large number of documents at home and abroad about polyarylate modification. For example, patents such as CN02817350.3, CN200680046533.7, US4804707, and US5149769 disclose methods for modifying polyarylates to obtain polyarylates with different properties. However, fluoropolysiloxane-polyarylate block copolymers prepared by hydrosilylation of fluorine-containing/fluorine-free polysiloxane and fluorine-containing/fluorine-free terminal olefin polyarylate are in No relevant reports have been found in the literature.

Contents of the invention

One of the objects of the present invention is to provide a polysiloxane-polyarylate block copolymer; the block copolymer has low surface energy, strong hydrophobicity, and obvious microphase separation structure. Esters have a wider range of applications.

The second object of the present invention is to provide a preparation method of the polysiloxane-polyarylate block copolymer; the preparation method is simple and easy to operate.

The third object of the present invention is to provide the application of the above-mentioned polysiloxane-polyarylate block copolymer in the field of materials.

The present invention is achieved through the following technical solutions:

A polysiloxane-polyarylate block copolymer with a structure as shown in formula 1:

Formula 1

In formula 1, m is a natural number of 15-200, n is _a natural number of 8-150, and n1 is a natural number of 8-150;

A is , , ,or ;

R is methyl or -CH ₂ CH ₂ CF ₃

_R1 is _-H or _{-CH2CH2CH2CH3 .}

The above-mentioned polysiloxane-polyarylate block copolymer, its number average molecular weight It is 8500~70000; its molecular weight distribution index is 2.1-3.1, its viscosity is 0.5~0.9dl/g, and the contact angle to water after film formation is greater than 105°; the preferred contact angle to water after film formation is 106-112 °.

The above-mentioned polysiloxane-polyarylate block copolymer is composed of fluorine-containing/non-fluorine-terminated olefin-based polyarylate and fluorine-containing/fluorine-free hydrogen-terminated polysiloxane in a solvent through hydrosilylation prepared by method.

A method for preparing the above-mentioned polysiloxane-polyarylate block copolymer: using fluorine-containing/fluorine-free olefin-terminated polyarylate and fluorine-containing/non-fluorine-containing hydrogen-terminated polysiloxane as raw materials, One or more of tetrahydrofuran, isopropanol, toluene and trifluorotoluene are used as solvents; catalyst 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum ( 0) (Karstedt platinum catalyst) or hydrosilylation under the action of chloroplatinic acid. Wherein, the structural formula of the terminal olefin polyarylate is:

,

A is , , ,or ;

m is a natural number from 15 to 200; it is prepared by interfacial polymerization of bisphenol compound, terephthaloyl chloride, isophthaloyl chloride and end-capping agent allyl chloride. The number average molecular weight of the hydrogen-terminated polysiloxane is 1000~10000, selected from single-ended hydrogen polydimethylsiloxane, single-ended hydrogen polymethyltrifluoropropylsiloxane, double-ended hydrogen polydimethylsiloxane, One or more of base siloxane and double-terminal hydrogen polymethyltrifluoropropyl siloxane.

The specific preparation method of the above-mentioned polysiloxane-polyarylate block copolymer is as follows: firstly, under the condition of 0-30°C, add the hydrogen-terminated polysiloxane and 2/5 of the solvent into the reaction bottle, stir well , then add the catalyst diluted with 1/5 of the solvent, and finally add the remaining solvent and olefin-terminated polyarylate, stir for 15-30 minutes, raise the temperature to 60-80°C for 1-5 hours, and remove the solvent; A polysiloxane-polyarylate block copolymer is obtained. Wherein, the molar ratio of the olefin-terminated polyarylate, the hydrogen-terminated polysiloxane and the catalyst is 1:1~2:0.00021~0.00048; the quality of the solvent is the total mass of the olefin-terminated polyarylate and the hydrogen-terminated polysiloxane 1~4 times. Wherein, the amount of solvent used each time is calculated based on the total amount of solvent; wherein, 2/5 and 1/5 of the solvent refer to 2/5 and 1/5 of the total amount of solvent.

One of the polysiloxane-polyarylate block copolymers described above is used to prepare hemocompatible coatings.

Beneficial effect

One, polysiloxane-polyarylate block copolymer of the present invention, its surface has lower surface energy, and hydrophobicity is strong; Has obvious microphase separation structure, has broader than traditional polyarylate Wide range of applications, can be used as blood compatible material;

2. The method for preparing polysiloxane-polyarylate block copolymer is simple, the reaction conditions are mild and easy to control, and it is easy to industrialized production;

3. When the polysiloxane-polyarylate block copolymer is used as a blood-compatible material, compared with traditional blood-compatible materials such as polyvinyl chloride, it can significantly prolong the coagulation time and effectively reduce the adhesion of platelets.

Detailed ways

The present invention is illustrated by specific examples below, but the present invention is not limited to these examples.

Example 1

Preparation of olefin-terminated polyarylate: First, add 0.03mol (6.84g) of bisphenol A, 0.066mol (2.64g) of NaOH, 80ml of deionized water and 0.051g of phase transfer catalyst into a three-necked flask, and stir to dissolve bisphenol A It forms an inorganic phase in water. Dissolve 0.015mol (3.03g) of terephthaloyl chloride and isophthaloyl chloride in 150ml of dichloromethane to form an organic phase with a certain concentration. Slowly drop the organic phase into the inorganic phase at a temperature of 10°C. After stirring and reacting for 2 hours, slowly add 0.0035mol (0.317g) of acryloyl chloride monomer dropwise at 10°C. The following reaction was carried out for 1 hour. Remove dichloromethane and water, and obtain terminal olefin-based polyarylate after drying, and use GPC-MwA gel chromatography to measure the number-average molecular weight of polyarylate for 6300.

Preparation of polysiloxane-polyarylate block copolymer: Add 2 g (0.002 mol) of single-terminal hydrogen polymethyltrifluoropropylsiloxane and 10 g of benzotrifluoride into the reaction flask at 0 °C, Stir well. Dissolve 0.02g of the Karstedt platinum catalyst in 5g of benzotrifluoride, then add it to the reaction flask, and finally add the olefin-terminated polyarylate benzofluoride solution (6.3g of the olefin-terminated polyarylate prepared above, 10g of benzotrifluoride) , after stirring for 15 minutes, the temperature was raised to 80° C., and reacted for 2 hours. After the reaction was complete, the solvent was removed to obtain polysiloxane-polyarylate block copolymer.

The intrinsic viscosity of the copolymer measured by Ubbelohde's viscometer was 0.58dl/g. The number average molecular weight of the copolymer was measured by GPC-MwA gel chromatography 8500, molecular weight distribution index =2.1; The contact angle of the copolymer with water after film formation is measured by a German OCA contact angle measuring instrument to be 106°.

Example 2

Preparation of fluorine-containing polyarylate with terminal olefin group: First, add bisphenol AF0.03mol (10.14g), 0.066mol (2.64g) NaOH, 80ml deionized water and 0.051g phase transfer catalyst in a three-necked flask, stir to make bisphenol AF is dissolved in water to form an inorganic phase. Dissolve 0.02mol (4.05g) of terephthaloyl chloride and 0.01mol (2.03g) of isophthaloyl chloride in 150ml of dichloromethane to form an organic phase with a certain concentration. Slowly drop the organic phase into the inorganic phase at a temperature of 0°C. After stirring for 5 hours, slowly add 0.0035mol (0.317g) of acryloyl chloride monomer dropwise at 0°C. The following reaction was carried out for 1 hour. Remove dichloromethane and water, and obtain olefin-terminated fluorine-containing polyarylate after drying, and use GPC-MwA gel chromatography to measure the number-average molecular weight of olefin-terminated fluorine-containing polyarylate for 48000.

Preparation of polysiloxane-polyarylate block copolymer: Add 10 g (0.01 mol) of double-terminated hydrogen polydimethylsiloxane and 10 g of tetrahydrofuran into a reaction flask at 0° C., and stir evenly. Dissolve 0.03g of the Karstedt platinum catalyst in 5g of tetrahydrofuran, then add it to the reaction flask, and finally add the olefin-terminated polyarylate tetrahydrofuran solution (wherein the above-mentioned prepared olefin-terminated polyarylate 48g, tetrahydrofuran 120g), after stirring for 30 minutes, the The temperature was raised to 60° C. and reacted for 5 hours. After the reaction was complete, the solvent was removed to obtain a polysiloxane-polyarylate block copolymer.

The intrinsic viscosity of the copolymer measured by Ubbelohde's viscometer was 0.82dl/g. The number average molecular weight of the copolymer was measured by GPC-MwA gel chromatography 70000, molecular weight distribution index =2.4; The contact angle of the copolymer with water after film formation was measured by a German OCA contact angle measuring instrument to be 110°.

Example 3

Preparation of fluorine-containing polyarylate with terminal olefin group: First, add bisphenol AF0.03mol (10.14g), 0.066mol (2.64g) NaOH, 80ml deionized water and 0.051g phase transfer catalyst in a three-necked flask, stir to make bisphenol AF is dissolved in water to form an inorganic phase. Dissolve 0.01mol (2.03g) of terephthaloyl chloride and 0.02mol (4.05g) of isophthaloyl chloride in 150ml of dichloromethane to form an organic phase with a certain concentration. Slowly drop the organic phase into the inorganic phase at a temperature of 5°C. After stirring and reacting for 3 hours, slowly add 0.0035mol (0.317g) of acryloyl chloride monomer dropwise at 0°C. The following reaction was carried out for 5 hours. Remove dichloromethane and water, and obtain olefin-terminated fluorine-containing polyarylate after drying, and use GPC-MwA gel chromatography to measure the number-average molecular weight of olefin-terminated fluorine-containing polyarylate for 17000.

Preparation of polysiloxane-polyarylate block copolymer: at 5°C, add 5g (0.001mol) of double-terminal hydrogen polymethyltrifluoropropylsiloxane and 10g of toluene into the reaction flask, and stir evenly . Dissolve 0.04g of the Karstedt platinum catalyst in 5g of toluene, then add it to the reaction flask, and finally add the tetrahydrofuran solution of olefin-terminated fluorine-containing polyarylate (including 17g of the above-prepared olefin-terminated polyarylate and 80g of toluene), and stir for 30 minutes , raise the temperature to 70°C, and react for 4 hours. After the reaction is complete, remove the solvent to obtain polysiloxane-polyarylate block copolymer.

The intrinsic viscosity of the copolymer measured by Ubbelohde's viscometer was 0.64dl/g. The number average molecular weight of the copolymer was measured by GPC-MwA gel chromatography 43000, molecular weight distribution index =3.1; The contact angle of the copolymer with water after film formation was measured by a German OCA contact angle measuring instrument to be 112°.

Claims (10)

1. structure polysiloxane-polyarylate segmented copolymer as shown in Equation 1:

Formula 1

In formula 1, m is the natural number of 15-200, and n is the natural number of 8-150, n ₁for the natural number of 8-150;

A is , , , or ;

R is methyl or-CH ₂cH ₂cF ₃

R1 is-H or-CH ₂cH ₂cH ₂cH ₃.

2. polysiloxane-polyarylate segmented copolymer according to claim 1, is characterized in that, its number-average molecular weight be 8500 ~ 70000.

3. polysiloxane-polyarylate segmented copolymer according to claim 1 and 2, is characterized in that, its molecular weight distributing index is 2.1-3.1, and its viscosity is 0.5 ~ 0.9dL/g, is greater than 105 ° after film forming to the contact angle of water.

4. polysiloxane-polyarylate segmented copolymer according to claim 3, is characterized in that, is 106-112 ° to the contact angle of water after its film forming.

5. polysiloxane-polyarylate segmented copolymer according to claim 4, is characterized in that, is to be prepared from by Si―H addition reaction method in a solvent by fluorine-containing/not fluorine-containing terminal olefine base polyarylester and fluorine-containing/not fluorine-containing end hydrogen polysiloxanes.

6. the preparation method of polysiloxane-polyarylate segmented copolymer described in a Claims 1 to 5 any one, it is characterized in that, with fluorine-containing/not fluorine-containing terminal olefine base polyarylester and fluorine-containing/not fluorine-containing end hydrogen polysiloxanes for raw material, with one or more in tetrahydrofuran (THF), Virahol, toluene and phenylfluoroform for solvent; Si―H addition reaction under the effect of catalyzer 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0) or Platinic chloride.

7. preparation method according to claim 6, is characterized in that: the structural formula of described terminal olefine polyarylester is:

，

A is , , , or ;

M is the natural number of 15-200; Be prepared from by interfacial polymerization by bisphenol type compounds, p-phthaloyl chloride, m-phthaloyl chloride and end-capping reagent allyl group acyl chlorides.

8. preparation method according to claim 6, it is characterized in that: the number-average molecular weight of described end hydrogen polysiloxanes is 1000 ~ 10000, be selected from single-ended hydrogen polydimethylsiloxane, single-ended hydrogen gathers methyl trifluoro propyl siloxanes, both-end hydrogen polydimethylsiloxane and both-end hydrogen gather in methyl trifluoro propyl siloxanes one or more.

9. the preparation method according to claim 6,7 or 8, it is characterized in that: first, under the condition of 0 ~ 30 DEG C, the solvent of end hydrogen polysiloxanes and 2/5 is added in reaction flask, stirs, then add the catalyzer after with the solvent cut of 1/5, finally add remaining solvent and terminal olefine polyarylester, stir after 15 ~ 30 minutes, temperature is risen to 60 ~ 80 DEG C of reactions 1 ~ 5 hour, except desolventizing; Obtain polysiloxane-polyarylate segmented copolymer;

Wherein, the mol ratio of described terminal olefine polyarylester, end hydrogen polysiloxanes and catalyzer is 1:1 ~ 2:0.00021 ~ 0.00048; The quality of solvent is the total mass 1 ~ 4 times that terminal olefine polyarylester and end hydrogen gather silica.

10. a purposes for the polysiloxane-polyarylate segmented copolymer described in Claims 1 to 5 any one, is characterized in that, for the preparation of blood compatibility coating.