阅读说明：本技术 一种改性玻璃纤维及应用、增强苯乙烯马来酸酐共聚物组合物及其制备方法 (Modified glass fiber and application thereof, reinforced styrene maleic anhydride copolymer composition and preparation method thereof ) 是由 黄伟 李德锋 于 2020-05-29 设计创作，主要内容包括：本发明公开了一种改性玻璃纤维及应用、增强苯乙烯马来酸酐共聚物组合物及其制备方法,本发明所述的改性玻璃纤维是经过用稀土化合物表面改性得到的,可以用于苯乙烯马来酸酐共聚物的增强改性中,可明显改善苯乙烯马来酸酐共聚物的物理机械性能和表面浮纤问题,同时提高材料的加工脱模性。所述增强苯乙烯马来酸酐共聚物组合物,包括以下成分：苯乙烯马来酸酐共聚物、上述改性玻璃纤维、硅酮母粒和其他助剂。通过稀土化合物改性后的改性玻璃纤维与由硅酮粉、氯化镧和苯乙烯马来酸酐共聚物制得的硅酮母粒共同作用下,可以明显改善苯乙烯马来酸酐共聚物的物理机械性能和表面浮纤问题,并且能显著提高加工脱模性,可以广泛用于汽车零部件材料领域中。(The invention discloses a modified glass fiber and application thereof, a reinforced styrene maleic anhydride copolymer composition and a preparation method thereof. The reinforced styrene maleic anhydride copolymer composition comprises the following components: styrene maleic anhydride copolymer, the modified glass fiber, silicone master batch and other auxiliary agents. Under the combined action of the modified glass fiber modified by the rare earth compound and the silicone master batch prepared from the silicone powder, lanthanum chloride and the styrene maleic anhydride copolymer, the physical and mechanical properties and the surface fiber floating problem of the styrene maleic anhydride copolymer can be obviously improved, the processing and demolding properties can be obviously improved, and the modified glass fiber modified by the rare earth compound can be widely applied to the field of automobile part materials.)

1. A modified glass fiber characterized by:

the modified glass fiber is obtained by surface modification with rare earth compounds.

2. The modified glass fiber of claim 1, prepared by the process of:

adding glass fiber into water containing an emulsifier, stirring and emulsifying, adding a rare earth compound aqueous solution, stirring and reacting for 30min, introducing ammonia water, washing with water, dehydrating and drying to obtain modified glass fiber;

the rare earth compound aqueous solution is a mixed solution of 30 parts by weight of a 10 wt% lanthanum chloride aqueous solution and 20 parts by weight of a 10 wt% cerium chloride aqueous solution.

3. The modified glass fiber of claim 2, prepared by the process of:

adding glass fiber into distilled water containing an emulsifier, stirring and emulsifying, keeping the temperature at 70-80 ℃, then uniformly dropwise adding the rare earth compound aqueous solution consisting of 30 parts by weight of 10 wt% lanthanum chloride aqueous solution and 20 parts by weight of 10 wt% cerium chloride aqueous solution, wherein the dropwise adding speed of the rare earth compound aqueous solution is 5 parts by weight/10 min, stirring for 30min at 70-80 ℃ after dropwise adding, then introducing ammonia water and keeping stirring, centrifuging after 2h, washing for 3-4 times with distilled water, and drying for 8h at 80 ℃ after dehydrating to obtain the modified glass fiber.

4. The modified glass fiber of claim 3, wherein:

the diameter of the glass fiber is 13-15 μm.

5. Use of the glass fiber according to any of claims 1 to 4 for reinforcing styrene maleic anhydride copolymers.

6. The reinforced styrene maleic anhydride copolymer composition according to claim 5, comprising the following components in parts by weight:

63-76.4 parts of styrene maleic anhydride copolymer;

18.6 to 35 parts by weight of the modified glass fiber of claim 1, 2 or 3;

1-5 parts of silicone master batch;

0-1 part of other auxiliary agents.

7. The reinforced styrene maleic anhydride copolymer composition of claim 6, wherein:

the styrene maleic anhydride copolymer is prepared by the following method:

weighing styrene and maleic anhydride, wherein the weight ratio of the styrene to the maleic anhydride is 75: (20-30), dissolving maleic anhydride in styrene, adding N-phenylmaleimide, wherein the weight of the N-phenylmaleimide is 15 percent of that of the styrene, putting the mixture into a reaction kettle, reacting at the temperature of 100-120 ℃ for 8 hours at normal temperature, and then extruding and granulating the mixture by a double-screw extruder to obtain the styrene-maleic anhydride copolymer.

8. The reinforced styrene maleic anhydride copolymer composition of claim 7, wherein:

the silicone master batch is prepared by the following method:

mixing silicone powder and soluble lanthanum salt (lanthanum chloride) according to the proportion of (1-3): 100, stirring for 10-30 minutes at 70 ℃ at a stirring speed of 200 revolutions per minute to obtain lanthanum compound modified silicone powder;

mixing a lanthanide modified silicone powder and the styrene maleic anhydride copolymer in a ratio of 1: 1, melting and extruding in a double-screw extruder at the extrusion temperature of 170-200 ℃, and extruding and granulating to obtain the silicone master batch.

9. The reinforced styrene maleic anhydride copolymer composition of claim 8, wherein:

the other auxiliary agents comprise an antioxidant which is selected from one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], zinc oxide and tris (2, 4-di-tert-butylphenol) phosphite.

10. A process for the preparation of the reinforced styrene maleic anhydride copolymer composition according to any one of claims 5 to 9, wherein:

(1) weighing styrene maleic anhydride copolymer, silicone master batch and other additives according to the proportion, mixing for 3-5min in a high-speed mixer, and adding into a double-screw extruder at a first section after uniformly mixing;

(2) feeding modified glass fiber at the third section side of the double screw;

(3) the composition is obtained after melt extrusion, granulation and drying.

Technical Field

The invention belongs to the field of high molecular polymers, and particularly relates to a modified glass fiber and application thereof, a reinforced styrene maleic anhydride copolymer composition and a preparation method thereof.

Background

Styrene maleic anhydride copolymers are obtained by free radical polymerization of styrene and maleic anhydride. It is used as the most economical product in important applications of structural parts in automobiles, and is widely used in industry.

Glass fiber reinforced styrene maleic anhydride copolymer (SMA) is mainly used for parts in the automotive field, such as automobile instrument panel frameworks, skylight frameworks and the like, but the application of the SMA is influenced because the SMA is brittle due to lower physical and mechanical properties, particularly impact strength. Further, since the glass fiber-reinforced styrene-maleic anhydride copolymer is often a bulky part in injection molding, the processing releasability thereof is poor. In addition, because the polarity of the glass fiber and the SMA is greatly different, the glass fiber is easily exposed on the surface of the SMA matrix to form 'floating fiber' after the two are blended, and the appearance is poor.

Disclosure of Invention

The invention aims to provide a modified glass fiber which can be used for reinforcing a styrene maleic anhydride copolymer, can obviously improve the physical and mechanical properties and the surface fiber floating problem of the styrene maleic anhydride copolymer, and simultaneously improves the processing and demolding properties of materials.

Further, the invention also provides application of the modified glass fiber.

Further, the invention also provides a reinforced styrene maleic anhydride copolymer composition which has good physical and mechanical properties and can obviously improve the surface floating fiber problem and processing demoulding property.

Further, the invention also provides a preparation method of the reinforced styrene maleic anhydride copolymer composition.

A modified glass fiber is obtained by surface modification with rare earth compounds.

The modified glass fiber is prepared by the following method:

adding glass fiber into water containing an emulsifier, stirring and emulsifying, adding a rare earth compound aqueous solution, stirring and reacting for 30min, introducing ammonia water, washing with water, dehydrating and drying to obtain modified glass fiber;

the rare earth compound aqueous solution is a mixed solution of 30 parts by weight of a 10 wt% lanthanum chloride aqueous solution and 20 parts by weight of a 10 wt% cerium chloride aqueous solution.

Preferably, the modified glass fiber is prepared by the following method:

adding glass fiber into distilled water containing an emulsifier, stirring and emulsifying, keeping the temperature at 70-80 ℃, then uniformly dropwise adding the rare earth compound aqueous solution consisting of 30 parts by weight of 10 wt% lanthanum chloride aqueous solution and 20 parts by weight of 10 wt% cerium chloride aqueous solution, wherein the dropwise adding speed of the rare earth compound aqueous solution is 5 parts by weight/10 min, stirring for 30min at 70-80 ℃ after dropwise adding, then introducing ammonia water and keeping stirring, centrifuging after 2h, washing for 3-4 times with distilled water, and drying for 8h at 80 ℃ after dehydrating to obtain the modified glass fiber.

More preferably, the modified glass fiber is prepared by the following method:

adding 10 parts by weight of glass fiber into 80-95 parts of distilled water containing 2-5 wt% of emulsifier, stirring and emulsifying, keeping the temperature at 70-80 ℃, then uniformly dropwise adding the rare earth compound aqueous solution consisting of 30 parts by weight of 10 wt% lanthanum chloride aqueous solution and 20 parts by weight of 10 wt% cerium chloride aqueous solution, wherein the dropwise adding speed of the rare earth compound aqueous solution is 5 parts by weight/10 min, stirring for 30min at 70-80 ℃ after dropwise adding, then introducing ammonia water and keeping stirring, centrifuging and washing for 3-4 times with distilled water after 2h, and drying for 8h at 80 ℃ after dehydration to obtain the modified glass fiber.

More preferably, the modified glass fiber is prepared by the following method:

adding 10 parts by weight of glass fiber into 90 parts of distilled water containing 3 wt% of emulsifier, stirring and emulsifying, keeping the temperature at 70-80 ℃, then uniformly dropwise adding the rare earth compound aqueous solution consisting of 30 parts by weight of 10 wt% lanthanum chloride aqueous solution and 20 parts by weight of 10 wt% cerium chloride aqueous solution, wherein the dropwise adding speed of the rare earth compound aqueous solution is 5 parts by weight/10 min, stirring for 30min at 70-80 ℃ after dropwise adding, then introducing ammonia water and keeping stirring, centrifuging and washing for 3-4 times with distilled water after 2h, and drying for 8h at 80 ℃ after dehydration to obtain the modified glass fiber.

Preferably, the glass fibers have an average diameter of 13 to 15 μm, preferably 13 μm.

The application of the modified glass fiber in reinforcing styrene maleic anhydride copolymer can obviously improve the physical and mechanical properties and the surface fiber floating problem of the reinforced styrene maleic anhydride copolymer and obviously improve the processing and demolding properties of the reinforced styrene maleic anhydride copolymer.

A reinforced styrene maleic anhydride copolymer composition comprising the following ingredients:

styrene maleic anhydride copolymers;

the above-mentioned modified glass fiber;

silicone master batches;

and (3) other auxiliary agents.

Preferably, the reinforced styrene maleic anhydride copolymer composition comprises the following components in parts by weight:

63-76.4 parts of styrene maleic anhydride copolymer;

18.6 to 35 parts by weight of the modified glass fiber;

1-5 parts of silicone master batch;

0-1 part of other auxiliary agents.

Preferably, the sum of the parts by weight of the above components is 100 parts by weight.

Preferably, the reinforced styrene maleic anhydride copolymer composition consists of the following components in parts by weight:

73.3 parts by weight of a styrene maleic anhydride copolymer;

24.2 parts by weight of the modified glass fiber;

2 parts of silicone master batch;

0.5 part of other auxiliary agents.

Preferably, the styrene maleic anhydride copolymer is prepared by the following method:

weighing styrene and maleic anhydride, wherein the weight ratio of the styrene to the maleic anhydride is 75: (20-30), dissolving maleic anhydride in styrene, adding N-phenylmaleimide accounting for 12-16% of the weight of the styrene, putting the mixture into a reaction kettle, reacting at the temperature of 100-120 ℃ for 8 hours at normal temperature, and extruding and granulating by a double-screw extruder to obtain the styrene maleic anhydride copolymer.

More preferably, the styrene maleic anhydride copolymer is prepared by the following method:

weighing styrene and maleic anhydride, wherein the weight ratio of the styrene to the maleic anhydride is 75:25, dissolving maleic anhydride in styrene, adding N-phenylmaleimide, wherein the weight of the N-phenylmaleimide is 15 percent of that of the styrene, putting the mixture into a reaction kettle, reacting at the temperature of 100-120 ℃ for 8 hours at normal temperature, and then extruding and granulating by a double-screw extruder to obtain the styrene maleic anhydride copolymer.

Preferably, the silicone master batch is prepared by the following method:

mixing silicone powder and soluble lanthanum compound with the ratio of (1-3): 100, stirring for 10-30 minutes at 70 ℃ at a stirring speed of 200 revolutions per minute to obtain lanthanum compound modified silicone powder;

mixing a lanthanide modified silicone powder and the styrene maleic anhydride copolymer in a ratio of 1: 1, melting and extruding in a double-screw extruder at the extrusion temperature of 170-200 ℃, and extruding and granulating to obtain the silicone master batch.

Preferably, the silicone master batch is prepared by the following method:

mixing silicone powder and lanthanum chloride in a ratio of (1-3): 100, and stirring for 10-30 minutes at 70 ℃ at a stirring speed of 200 revolutions per minute to obtain lanthanum chloride modified silicone powder;

mixing lanthanum chloride modified silicone powder and the styrene maleic anhydride copolymer in a ratio of 1: 1, melting and extruding in a double-screw extruder at the extrusion temperature of 170-200 ℃, and extruding and granulating to obtain the silicone master batch.

The rare earth compound has an f-orbital, and not only has oxophilicity, but also has high Lewis acidity. The rare earth ions are easy to complex with hydroxyl and other functional groups on the surface of the glass fiber, so that the rare earth compound is firmly attached to the surface of the glass fiber, and the treated glass fiber is added into the polymer, so that the effect of the rare earth compound can be fully exerted. Under the combined action of the modified glass fiber modified by the rare earth compound and the silicone master batch, the physical and mechanical properties and the surface fiber floating problem of the styrene maleic anhydride copolymer can be obviously improved, and the processing and demolding properties of the styrene maleic anhydride copolymer can be obviously improved.

Preferably, the other auxiliary agent comprises an antioxidant selected from one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], zinc oxide and tris (2, 4-di-tert-butylphenol) phosphite.

The preparation method of the reinforced styrene maleic anhydride copolymer composition,

(1) weighing styrene maleic anhydride copolymer, silicone master batch and other additives according to the proportion, mixing for 3-5min in a high-speed mixer, and adding into a double-screw extruder at a first section after uniformly mixing;

(2) feeding modified glass fiber at the third section side of the double screw;

(3) the composition is obtained after melt extrusion, granulation and drying.

Preferably, the melt extrusion conditions are: 200 ℃ and 240 ℃; the length-diameter ratio of the twin-screw extruder is 40: 1.

Compared with the prior art, the composition provided by the invention is prepared by co-melting and extruding the styrene maleic anhydride copolymer, the modified glass fiber, the silicone master batch and other auxiliary agents. Under the combined action of the modified glass fiber modified by the rare earth compound and the silicone master batch prepared from the silicone powder, lanthanum chloride and the styrene maleic anhydride copolymer, the physical and mechanical properties and the surface fiber floating problem of the styrene maleic anhydride copolymer can be obviously improved, the processing and demolding properties of the styrene maleic anhydride copolymer can be obviously improved, and the modified glass fiber modified by the rare earth compound can be widely applied to the field of automobile part materials.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments in order to make the technical field better understand the scheme of the present invention.