CN107057067B

CN107057067B - Triblock reactive compatilizer and preparation method thereof

Info

Publication number: CN107057067B
Application number: CN201611255365.4A
Authority: CN
Inventors: 张才亮; 王笛; 吴坤红; 冯连芳; 顾雪萍; 王嘉骏
Original assignee: Zhejiang University ZJU
Current assignee: Hangzhou Jufeng New Material Co ltd
Priority date: 2016-12-30
Filing date: 2016-12-30
Publication date: 2020-04-24
Anticipated expiration: 2036-12-30
Also published as: CN107057067A

Abstract

The invention discloses a triblock reactive compatilizer and a preparation method thereof, wherein the compatilizer comprises three parts: the polymer blend has one segment compatible with one phase in the polymer blend system, one reactive functional group capable of reacting with the other phase in the polymer blend system to form a copolymer, and three segments incompatible with the polymer blend components. Because the compatilizer has chain segments which are incompatible with polymer blending components, the compatilizer not only can easily reach the interface for reaction, but also can stabilize the formed copolymer at the interface, thereby reducing the using amount of the compatilizer. The invention is applied to the melt blending reaction of polysiloxane and nylon, the compatilizer can easily reach the interface, so that the amino at the tail end can react with the nylon to generate the nylon-polyether-polysiloxane copolymer, the nylon-polyether-polysiloxane copolymer can be stabilized at the interface, the interfacial tension between polymers is reduced, the reaction compatibilization is realized, the polysiloxane can be promoted to be dispersed in the nylon, and the performance of the blend is effectively improved.

Description

Triblock reactive compatilizer and preparation method thereof

Technical Field

The invention relates to the field of polymer material processing, in particular to a triblock reactive compatilizer and a preparation method thereof.

Background

Polymer blending is currently an important method for preparing high performance polymer materials. However, most polymers are thermodynamically incompatible and tend to phase separate, resulting in a substantial reduction in the final product properties. Therefore, in order to obtain more polymer blend materials with practical value, the key problem is to perform compatibilization modification on an incompatible blend system, improve the interfacial adhesion between a dispersed phase and a matrix and disperse the dispersed phase in the matrix with tiny particle size.

Early improvement of the compatibility between incompatible polymers was mainly achieved by adding the copolymer directly as a compatibilizer. However, this method has a problem that the copolymer alone tends to form micelles during blending and does not reach the interface efficiently, in addition to the difficulty in synthesizing the copolymer. The most common method at present is reactive compatibilization, i.e. the in situ generation of graft or block copolymers by interfacial reactions during blending serves for compatibilization. Although this approach solves the problem of the compatibilizer reaching the interface, the in situ generated copolymer may leave the interface, resulting in higher amounts of compatibilizer that affect the final properties of the blend.

Disclosure of Invention

The invention aims to overcome the defects and shortcomings in the prior art and provides a triblock reactive compatilizer and a preparation method thereof.

The triblock reactive compatibilizer provided by the invention comprises three parts: the polymer blend has one segment compatible with one phase in the polymer blend system, one reactive functional group capable of reacting with the other phase in the polymer blend system to form a copolymer, and three segments incompatible with the polymer blend components. The chain segment incompatible with the polymer blending components can well stabilize the formed copolymer at the interface, and the dosage of the compatilizer is reduced.

The invention focuses on a nylon/polysiloxane blending system, and the preparation steps of the triblock reactive compatilizer for the nylon/polysiloxane blending system are as follows: (1) preparing a hydrosilylene-terminated polysiloxane; (2) preparing epoxy-terminated polysiloxane by hydrosilylation reaction; (3) the polyether is attached to the polysiloxane by reacting the epoxy functional group with the amino group to form a triblock reactive phase solvent.

The preparation step (1) of the triblock reactive compatilizer for the nylon/polysiloxane blending system comprises the following steps: under the protection of nitrogen, polysiloxane monomer, silicon hydride terminated siloxane and catalyst are added into a reaction kettle in sequence, stirred for reaction, and finally dried after being settled by methanol.

The preparation method of the triblock reactive compatilizer for the nylon/polysiloxane blending system comprises the following steps (1), wherein the raw materials comprise the following components in parts by mass: 100 parts of polysiloxane monomer, 0.1-8 parts of hydrosilyl terminated siloxane and 0.01-0.1 part of catalyst.

The preparation step (1) of the triblock reactive compatilizer for the nylon/polysiloxane blending system is that the polysiloxane monomer can be hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and the like.

The preparation step (1) of the triblock reactive compatilizer for a nylon/polysiloxane blending system is that the hydrosilyl terminated siloxane can be tetramethyldihydrodisiloxane.

The preparation step (1) of the triblock reactive compatilizer for the nylon/polysiloxane blending system is that the catalyst is acidic cationic resin, and can be acid clay, sulfonic acid type cationic resin and the like.

The preparation step (2) of the triblock reactive compatilizer for the nylon/polysiloxane blending system comprises the following steps: adding allyl glycidyl ether and a catalyst into toluene, heating to 75 ℃, slowly dripping the hydrosilyl-terminated polysiloxane prepared in the step (1) into a reaction system at a slow speed, continuing to react for 3-8h after dripping, and finally settling and drying by methanol.

The preparation method of the triblock reactive compatilizer for the nylon/polysiloxane blending system comprises a preparation step (2), wherein the preparation method comprises the following raw materials in parts by mass: 100 parts of hydrosilicon terminated polysiloxane, 1-20 parts of allyl glycidyl ether and 0.2-1 part of catalyst.

The preparation step (2) of the triblock reactive compatibilizer for nylon/polysiloxane blending system is that the catalyst is a platinum complex catalyst, and can be one of chloroplatinic acid-isopropanol, chloroplatinic acid-tetramethyldivinyldisiloxane or chloroplatinic acid-diethyl phthalate.

The preparation step (3) of the triblock reactive compatilizer for the nylon/polysiloxane blending system comprises the following steps: and (3) adding the epoxy functional group-terminated polysiloxane prepared in the step (2) and diamine group-terminated polyether into isopropanol, reacting at 50-80 ℃, and finally distilling under reduced pressure to remove the solvent and low-boiling-point substances.

And (3) preparing the triblock reactive compatilizer for the nylon/polysiloxane blending system, wherein the molar ratio of the epoxy functional group in the epoxy functional group-terminated polysiloxane prepared in the step (2) to the amino group of the diamine-terminated polyether is 2.1-3.0.

The preparation step (2) of the triblock reactive compatibilizer for the nylon/polysiloxane blending system is that the diamine terminated polyether can be one or two of a propylene oxide ether segment and a vinyl oxide ether segment with the molecular weight of 200-5000.

The preparation method of the nylon/polysiloxane blend comprises the following preparation steps: firstly, adding nylon, polysiloxane and the prepared triblock reactive compatilizer into an internal mixer or an extruder for melt mixing, wherein the blending temperature is 180 ℃ and 230 ℃, and the blending time is 5-10 minutes.

Because the polysiloxane and the nylon are two types of polymers which are not thermodynamically compatible, in order to obtain a satisfactory blending modification effect, the invention adopts the triblock reactive compatilizer as the compatilizer to prepare the blend, and during the preparation, the nylon, the polysiloxane and the compatilizer are firstly added into an internal mixer or an extruder for melt mixing, the blending temperature is 180-; in the process, when the polysiloxane and the nylon are melt blended, because the polyether chain segment is incompatible with the polysiloxane and the nylon, the compatilizer can easily reach an interface so that the amino at the tail end can react with the nylon to generate a nylon-polyether-polysiloxane copolymer which can be stabilized at the interface, the reactive compatibilization is realized, the interfacial tension between the two polymers is reduced, the dispersion of the polysiloxane in the nylon is promoted, and the performance of the blend is improved.

Compared with other types of compatilizers, the triblock reactive compatilizer provided by the invention can easily achieve the effect that the interface reacts with the polymer blending component to generate a copolymer, can be stabilized at a phase interface, and can realize the particle size reduction and uniform dispersion of polymer blending under the condition of low consumption.

Drawings

FIG. 1 is a scanning electron micrograph of nylon/polysiloxane prepared according to each example and comparative example.

Detailed Description

The technical solution of the present invention is further described below with reference to the accompanying drawings by specific embodiments so that the technical solution of the present invention can be more easily understood and appreciated. It should be noted that the specific embodiments of the present invention are not limited by these examples, and all technical solutions formed by equivalent or equivalent changes in raw materials, ratios, process conditions, etc. by those skilled in the art according to the spirit of the present invention fall within the scope of the claims of the present invention.

In the following examples, the test methods used were: a tensile test is carried out according to the method of GB1040-2006, and the tensile rate is 5 mm/min; and (3) testing the notch impact strength of the cantilever beam according to a GB1843-2008 method, and selecting a 1J pendulum bob.

[ example 1 ]

Under the protection of nitrogen, sequentially adding 100 parts of octamethylcyclotetrasiloxane, 1.3 parts of tetramethyldihydro disiloxane and 0.2 part of sulfonic acid type cationic resin catalyst into a reaction kettle, stirring and reacting at 55 ℃ for 7 hours, and then settling and drying by methanol to prepare the silicon-hydrogen terminated polysiloxane; then adding 3.5 parts of allyl glycidyl ether and 0.5 part of chloroplatinic acid-isopropanol catalyst into toluene, heating to 75 ℃, then slowly dropwise adding the prepared hydrosilicon-terminated polysiloxane into a reaction system at a slow speed of 100 parts, after 5 hours of reaction, settling and drying by methanol to prepare epoxy-terminated polysiloxane, finally adding 100 parts of the prepared epoxy-terminated polysiloxane and 20 parts of diamine-terminated polyether with the molecular weight of 600 into isopropanol, reacting at 80 ℃ for 6 hours, and then distilling under reduced pressure to remove a solvent and low-boiling-point substances to obtain the triblock reaction type compatilizer, wherein the label is A1. 80 parts of nylon 6, 20 parts of polysiloxane and 0.5 part of A1 were added to an internal mixer and melt blended at 230 ℃ for 8min to give a nylon/polysiloxane blend identified as B1.

[ example 2 ]

Under the protection of nitrogen, sequentially adding 100 parts of octamethylcyclotetrasiloxane, 7.2 parts of tetramethyldihydro disiloxane and 0.3 part of sulfonic acid type cationic resin catalyst into a reaction kettle, stirring and reacting at 55 ℃ for 7 hours, and then settling and drying by methanol to prepare the silicon-hydrogen terminated polysiloxane; then adding 17 parts of allyl glycidyl ether and 0.6 part of chloroplatinic acid-isopropanol catalyst into toluene, heating to 75 ℃, slowly dropwise adding the prepared hydrosilicon terminated polysiloxane into a reaction system at a slow speed of 100 parts, after 5 hours of reaction, settling by methanol, drying to prepare epoxy terminated polysiloxane, finally adding 100 parts of the prepared epoxy terminated polysiloxane and 90 parts of diamine terminated polyether with molecular weight of 900 into isopropanol, reacting at 80 ℃ for 6 hours, and then distilling under reduced pressure to remove solvent and low-boiling-point substances to obtain the triblock reaction type compatilizer, wherein the label is A2. 80 parts of nylon 6, 20 parts of polysiloxane and 0.5 part of A2 were added to an internal mixer and melt blended at 230 ℃ for 8min to give a nylon/polysiloxane blend identified as B2.

[ example 3 ]

Under the protection of nitrogen, sequentially adding 100 parts of octamethylcyclotetrasiloxane, 2.8 parts of tetramethyldihydro disiloxane and 0.2 part of sulfonic acid type cationic resin catalyst into a reaction kettle, stirring and reacting at 55 ℃ for 7 hours, and then settling and drying by methanol to prepare the silicon-hydrogen terminated polysiloxane; then adding 6.8 parts of allyl glycidyl ether and 0.5 part of chloroplatinic acid-isopropanol catalyst into toluene, heating to 75 ℃, slowly dropwise adding 100 parts of prepared hydrosilicon-terminated polysiloxane into a reaction system at a slow speed, reacting for 5 hours, settling by methanol, drying to prepare epoxy-terminated polysiloxane, finally adding 100 parts of prepared epoxy-terminated polysiloxane and 38 parts of diamine-terminated polyether with the molecular weight of 900 into isopropanol, reacting for 6 hours at 80 ℃, and distilling under reduced pressure to remove a solvent and low-boiling-point substances to obtain the triblock reaction type compatilizer, wherein the label is A3. 80 parts of nylon 6, 20 parts of polysiloxane and 0.5 part of A2 were added to an internal mixer and melt blended at 230 ℃ for 8min to give a nylon/polysiloxane blend identified as B3.

[ example 4 ]

Under the protection of nitrogen, sequentially adding 100 parts of octamethylcyclotetrasiloxane, 0.7 part of tetramethyldihydro disiloxane and 0.2 part of sulfonic acid type cationic resin catalyst into a reaction kettle, stirring and reacting at 55 ℃ for 7 hours, and then settling and drying by methanol to prepare the silicon-hydrogen terminated polysiloxane; then adding 1.7 parts of allyl glycidyl ether and 0.5 part of chloroplatinic acid-isopropanol catalyst into toluene, heating to 75 ℃, slowly dropwise adding 100 parts of prepared hydrosilicon-terminated polysiloxane into a reaction system at a slow speed, reacting for 5 hours, settling by methanol, drying to prepare epoxy-terminated polysiloxane, finally adding 100 parts of prepared epoxy-terminated polysiloxane and 10 parts of diamine-terminated polyether with the molecular weight of 900 into isopropanol, reacting for 6 hours at 80 ℃, and distilling under reduced pressure to remove a solvent and low-boiling-point substances to obtain the triblock reaction type compatilizer, wherein the label is A4. 80 parts of nylon 6, 20 parts of polysiloxane and 0.25 part of A2 were added to an internal mixer and melt blended at 230 ℃ for 8min to give a nylon/polysiloxane blend identified as B4.

[ example 5 ]

80 parts of nylon 6, 20 parts of polysiloxane and 0.5 part of A4 were added to an internal mixer and melt blended at 230 ℃ for 8min to give a nylon/polysiloxane blend identified as B5.

[ example 6 ]

80 parts of nylon 6, 20 parts of polysiloxane and 1 part of A4 were added to an internal mixer and melt blended at 230 ℃ for 8min to give a nylon/polysiloxane blend identified as B6.

Comparative example 1

80 parts of nylon 6 and 20 parts of polysiloxane were added to an internal mixer and melt blended at 230 ℃ for 8min to give a nylon/polysiloxane blend, identified as C1.

Comparative example 2

80 parts of nylon 6, 20 parts of polysiloxane and 1 part of a commercially available amino-terminated polysiloxane were added to an internal mixer and melt blended at 230 ℃ for 8min to give a nylon/polysiloxane blend, identified as C2.

Comparative example 3

80 parts of nylon 6, 20 parts of polysiloxane and 5 parts of a commercially available amino-terminated polysiloxane were added to an internal mixer and melt blended at 230 ℃ for 8min to give a nylon/polysiloxane blend, identified as C3.

Table 1 shows the molecular weights and distributions of the triblock reactive compatibilizers prepared in examples 1 to 4, and Table 2 shows the mechanical property comparisons of the nylon 6/polysiloxane blends prepared in example 2 and comparative example 1.

TABLE 1

TABLE 2

FIG. 1 compares the scanning electron micrographs of the nylon 6/polysiloxane blends prepared in the examples and comparative examples. As can be seen from FIG. 1, the dispersed phase size is smaller and more uniform with the addition of the triblock reactive compatibilizer provided by the present invention, and the dispersed phase size is very effectively reduced with the addition of only 0.5 wt%, relative to the blend without the compatibilizer (C1), the blend with 1 wt% amino terminated polysiloxane (C2), and the blend with 5 wt% amino terminated polysiloxane (C3).

In addition, it can be seen from table 2 that the mechanical properties of the copolymer can be effectively improved by using the triblock reactive compatibilizer provided by the present invention.

Claims

1. A triblock reactive compatibilizer suitable for nylon/polysiloxane blending systems is characterized in that: the compatilizer is prepared by the following steps: step (1) preparing a hydrosilyl-terminated polysiloxane; step (2) preparing epoxy-terminated polysiloxane by hydrosilylation reaction; and (3) reacting the epoxy functional group with amino to connect the polyether to the polysiloxane to form the triblock reactive compatibilizer.

2. The triblock reactive compatibilizer of claim 1, wherein: and (1) adding a polysiloxane monomer, hydrosilyl-terminated siloxane and a catalyst into a reaction kettle in sequence under the protection of nitrogen, stirring for reaction, and finally settling by using methanol and drying.

3. The triblock reactive compatibilizer of claim 2, wherein: in the step (1), the raw materials comprise the following components in parts by mass: 100 parts of polysiloxane monomer, 0.1-8 parts of hydrosilyl terminated siloxane and 0.01-0.1 part of catalyst.

4. The triblock reactive compatibilizer according to claim 2 or 3, wherein: the polysiloxane monomer is hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.

5. The triblock reactive compatibilizer according to claim 2 or 3, wherein: the hydrosilyl-terminated siloxane is tetramethyldihydrodisiloxane.

6. The triblock reactive compatibilizer according to claim 2 or 3, wherein: the catalyst is an acidic cationic resin.

7. The triblock reactive compatibilizer of claim 6, wherein: the catalyst is acid clay or sulfonic acid type cationic resin.

8. The triblock reactive compatibilizer of claim 1, wherein: the step (2) is: adding allyl glycidyl ether and a catalyst into toluene, heating to 75 ℃, then dropwise adding the hydrosilyl-terminated polysiloxane prepared in the step (1) into a reaction system at a slow speed, continuing to react for 3-8h after dropwise adding, and finally settling and drying by methanol.

9. The triblock reactive compatibilizer of claim 8, wherein: the raw materials comprise the following components in parts by mass: 100 parts of hydrosilicon terminated polysiloxane, 1-20 parts of allyl glycidyl ether and 0.2-1 part of catalyst.

10. The triblock reactive compatibilizer according to claim 8 or 9, wherein: the catalyst is a platinum complex catalyst.

11. The triblock reactive compatibilizer of claim 10, wherein: the catalyst is chloroplatinic acid-isopropanol, chloroplatinic acid-tetramethyldivinyldisiloxane, or chloroplatinic acid-diethyl phthalate.

12. The triblock reactive compatibilizer of claim 1, wherein: the step (3) is: and (3) adding the epoxy functional group-terminated polysiloxane prepared in the step (2) and diamine group-terminated polyether into isopropanol, reacting at 50-80 ℃, and finally distilling under reduced pressure to remove the solvent and low-boiling-point substances.

13. The triblock reactive compatibilizer of claim 12, wherein: the molar ratio of the epoxy functional group in the epoxy functional group-terminated polysiloxane prepared in the step (2) to the amino group in the diamine group-terminated polyether is 2.1-3.0.

14. The triblock reactive compatibilizer according to claim 12 or 13, wherein: the molecular weight of the diamine terminated polyether is 200-5000, and the diamine terminated polyether contains one or two of an oxypropylene ether chain segment and an oxyethylene ether chain segment.