CN105440559A - High-performance glass fiber-reinforced ABS composition and preparation method thereof - Google Patents
High-performance glass fiber-reinforced ABS composition and preparation method thereof Download PDFInfo
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- CN105440559A CN105440559A CN201510933270.2A CN201510933270A CN105440559A CN 105440559 A CN105440559 A CN 105440559A CN 201510933270 A CN201510933270 A CN 201510933270A CN 105440559 A CN105440559 A CN 105440559A
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- coupling agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention provides a high-performance glass fiber-reinforced ABS composition and a preparation method thereof. A maleic anhydride-grafted ABS blended material is used as a compatilizer so that interface coupling effects of ABS and glass fibers are improved and mechanical strength of the ABS composition is obviously improved. Through use of a silane coupling agent and use of silane coupling agent characteristics of reaction with groups on the surfaces of the glass fibers and with resin, an interfacial layer is formed between the glass fibers and the resin base. The interfacial layer can transmit stress so that adhesion between the glass fibers and resin is improved, a stable structure is formed and the dispersed phase and the continuous phase are uniform and have compatibility. The used silane coupling agent is an amino silane coupling agent. Through use of the amino silane coupling agent containing two or more amino groups, activity is high and adhesion between the glass fibers and resin is improved so that mechanical properties of the composite material are greatly improved.
Description
Technical field
The invention belongs to modified plastics field, especially relate to a kind of high-performance fiber glass reinforced ABS composition and method of making the same.
Background technology
Styrene butadiene-vinyl cyanide (ABS) resin is with the rigidity of vinyl cyanide and thermotolerance, the features such as the shock resistance of the glossiness of polystyrene and processibility and polyhutadiene, are widely used in the fields such as household electrical appliance, office equipment, instrument, communications and transportation, material of construction, household utensils and wrapping material.
Use glass fiber reinforced ABS can improve the mechanical property of matrix material further, and improve its heat resisting temperature.The mechanical property of glass fiber reinforced ABS depends on the cohesive strength of ABS and glass fibre to a great extent, because the bonding interface of resin and glass is poor, the enhancement of glass can not be given full play to, the composite material strength of formation, toughness, the poor-performings such as thermotolerance.
Klumperman etc. (W091/15543) once with styrene-maleic anhydride copolymer (SMA), ABS, AS and glass for raw material, the ABS mixture of blended system.This mixture improves vicat softening temperature, but modulus in flexure is too low, only has 5000MPa; And owing to adding a large amount of ABS and SMA, manufacturing cost rises.Some investigator adopts Methacrylate-butadiene-styrene (MBS), ABS, SMA, AS and glass as raw material, blended obtained ABS mixture, but which increases glass dip treating step, and complex process and cost provide further.
Therefore, the fiber glass reinforced ABS composite material developing a kind of excellent in mechanical performance seems particularly important, has the huge market space.
Summary of the invention
In view of this, the present invention is intended to propose a kind of high-performance fiber glass reinforced ABS composition and method of making the same, poor with the bonding interface solving resin and glass, the enhancement of glass can not be given full play to, the composite material strength formed, toughness, the poor-performings such as thermotolerance and complex process, high in cost of production problem.
For achieving the above object, technical scheme of the present invention is achieved in that
A kind of high-performance fiber glass reinforced ABS composition, by weight percentage, comprises following component: ABS resin: 62.4-84.4%, glass fibre: 10-30%, compatilizer: 1-5%, coupling agent: 0.1-1%, auxiliary agent 0.1-3%.
Further, described compatilizer is the ABS blend of maleic anhydride graft, and percentage of grafting is 1-12%, and its melting means is 1-5g/10min (200 DEG C, 5kg).Anhydride group has high chemical reactivity, can react extruding in Blending Processes with the surface hydroxyl of glass, thus strengthens interface coupled action.Maleic anhydride grafted ABS imparts ABS polarity, as long as add the bonding force that a small amount of maleic anhydride grafted ABS just can increase substantially ABS and glass, the tensile strength of reinforced ABS, flexural strength etc. is significantly improved.
Further, described ABS resin is vinyl cyanide, divinyl, cinnamic terpolymer, and wherein the weight percent content of divinyl is 10-55%, and the weight percent content of vinyl cyanide is 15-32%, and cinnamic weight percent content is 30-70%.
Further, the preparation method of described ABS resin is substance law or emulsion method.
Further, described glass fibre is the mixing of one or more of long glass fibres or short glass fiber; Preferably, described long glass fibres is alkali free glass fibre, and diameter is 10-16 μm; Preferably, the length of described short glass fiber is 0.2-10mm, and diameter is 8-20 μm.
Further, described coupling agent is silane coupling agent, and general formula is YSiX3, in formula, Y is non-hydrolytic group, and representative and polymer molecule have the active function groups of avidity or response capacity, preferably, Y is oxygen base, sulfydryl, vinyl, epoxy group(ing), amide group or aminopropyl; X represents the alkoxyl group that can be hydrolyzed, and preferably, X is halogen, alkoxyl group or acyloxy.Glass fiber reinforced materials is because be the complex body be made up of glass fibre and synthetic resins, two kinds of materials differ greatly, compatible problem is there is after being mixed with each other, in order to ensure the performance of plastics, the interfacial state between glass fibre and resin must be changed, improve the cohesive force at its interface as far as possible, and use silane coupling agent, utilize its have can with some radical reaction of fiberglass surfacing, again can with the feature of resin reaction, an interfacial layer is formed between glass fibre and resin matrix, interfacial layer can transmit stress, thus enhance bond strength between glass fibre and resin, form stable structure, make disperse phase and external phase even, namely the compatibilized both realizing.
Further, described silane coupling agent is amino-type silane coupling agent, and preferably, the number of amino groups that described amino-type silane coupling agent contains is more than 2 or 2.Its hydrolysis rate of silane coupling agent is taken at silicon can roll into a ball X, is then taken at carbon functional group Y with the reactive behavior of organic polymer.In the group of two class performance inequalities of silane coupling agent, the difference of X base can only affect hydrolysis rate, on the essentially no impact of the performance of matrix material; Y group then directly determines the effect of silane coupling agent.Only have when Y group can react with corresponding matrix resin, could bonding strength be improved.General requirement Y group can mix with resin and can play linked reaction, so, for different substrate materials or handling object, select applicable silane coupling agent most important.In addition, the silane coupling agent of two amino-type or polyamino type, its catalytic activity is higher, advantageously in the mechanical property improving matrix material.
Further, described auxiliary agent is the mixing of one or more in thermo-stabilizer, photostabilizer, processing aid, toner or pigment; Preferably, described thermo-stabilizer is selected from more than one in phenols, phosphorous acid esters, monothioester class; Preferably, described photostabilizer is hindered amines or UV light absorber; Preferably, described processing aid is more than one in low molecule ester class stearic acid, metallic soap (CABSt, Znst), stearic acid complex ester or amides (erucicamide).
The present invention also provides a kind of preparation method of high-performance fiber glass reinforced ABS composite material, it is characterized in that:
Comprise the steps:
(1) take ABS resin, compatilizer, coupling agent and auxiliary agent by weight percentage and mix 1-3min in high mixer; Mix, obtain Preblend;
(2) Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying, to obtain final product.
Further, the described condition melt extruded is: a district temperature 180-210 DEG C, two district temperature 190-220 DEG C, three district temperature 190-230 DEG C, four district temperature 190-240 DEG C, five district temperature 190-240 DEG C, six district temperature 190-240 DEG C, seven district temperature 190-240 DEG C, eight district temperature 190-240 DEG C, nine district temperature 190-240 DEG C, engine speed 250-600 rev/min; The length-to-diameter ratio of twin screw extruder is 40:1.
Relative to prior art, high-performance fiber glass reinforced ABS composition and method of making the same of the present invention has following advantage:
1) the present invention uses with the ABS blend of maleic anhydride graft for compatilizer, can the interface coupled action of reinforced ABS and glass, significantly improves the physical strength of ABS composition; In addition, by adding silane coupling agent, utilize its have can with some radical reaction of fiberglass surfacing, again can with the feature of resin reaction, between glass fibre and resin matrix formed an interfacial layer, interfacial layer can transmit stress, thus enhance bond strength between glass fibre and resin, form stable structure, make disperse phase and external phase evenly, the compatibilized both namely realizing.
2) silane coupling agent that the present invention uses is amino-type silane coupling agent, especially the amino-type silane coupling agent containing 2 amino or multiple amino is used, its activity is higher, more effectively enhance the bond strength between glass fibre and resin, thus the mechanical property of matrix material is significantly improved.
Embodiment
It should be noted that, when not conflicting, the embodiment in the present invention and the feature in embodiment can combine mutually.
The present invention is described in detail below in conjunction with embodiment.
In following examples and comparative example, the processing conditions that forcing machine melt extrudes is as follows: a district temperature 180-210 DEG C, two district temperature 190-220 DEG C, three district temperature 190-230 DEG C, four district temperature 190-240 DEG C, five district temperature 190-240 DEG C, six district temperature 190-240 DEG C, seven district temperature 190-240 DEG C, eight district temperature 190-240 DEG C, nine district temperature 190-240 DEG C, engine speed 250-600 rev/min; The length-to-diameter ratio of twin screw extruder is 40:1.
ABS resin is selected from the NF2200 of Taiwan, and roving glass fiber is selected from the ER13-2000-988A of megalith group, and its Fibre diameter is 13 μm, and linear density is 2000tex; Short glass fiber is selected from the ECS-13-4.5 series of ShenzhenYataida company, and the length of its glass fibre is 4.5mm, and diameter is 13 μm; Compatilizer is selected from the KT-2 of Sheyang Ketong Plastic Co., Ltd., and percentage of grafting is 1.3%, and its melting means is 3.5g/10min (200 DEG C, 5kg); Silane coupling agent is selected from the KH-550 of the Chinese Academy of Sciences, KH-560 and KH-602.
Embodiment 1-6, comparative example 4
A kind of high-performance fiber glass reinforced ABS composition, its composition of raw materials is as shown in table 1, and its preparation method comprises the following steps:
Take ABS resin, glass fibre, compatilizer, silane coupling agent and auxiliary agent by weight percentage and mix 1-3min in high mixer; Mix, obtain Preblend; Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying.Measure its performance, concrete data list in table 3.
Comparative example 1-3
A kind of ABS composition, its composition of raw materials is as shown in table 1, and its preparation method comprises the following steps:
Take ABS resin, glass fibre, compatilizer and auxiliary agent by weight percentage and mix 1-3min in high mixer; Mix, obtain Preblend; Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying.Measure its performance, concrete data list in table 3.
The fiber glass reinforced ABS composition that embodiment and comparative example obtain adopts iso standard to test its correlated performance:
The composition of raw materials (by weight percentage) of the fiber glass reinforced ABS composition of table 1 embodiment and comparative example
Silane coupling agent specification used in table 2 embodiment and comparative example
The performance data of the fiber glass reinforced ABS composition of table 3 embodiment and comparative example
By embodiment 1 and comparative example 1, embodiment 2 and comparative example 2, embodiment 3,4,5 and comparative example 3, contrast can be found out, after adding silane coupling agent, the mechanical property of matrix material significantly improves, this is because by using silane coupling agent, the bond properties of glass fibre and resin can be improved, thus improve the performance of matrix material.This phenomenon can be explained with theory of chemical bonds, this theory is thought: silane coupling agent contains two kinds of different chemical functional groups, its one end (X group) and inorganic materials, the silanol groups reaction as surfaces such as glass fibre, silicate, metal oxides generates covalent linkage; The other end (Y group) generates covalent linkage with superpolymer base-material or resin again, thus erects between inorganic substance and the interface of organic substance " molecular bridge ", and then two kinds of inconsistent material couplings is got up.In addition, with suitable silane coupling agent process fiberglass surfacing, its surface tension can be improved, thus impel organic resin in the infiltration of mineral surfaces and expansion, convergency and the processing characteristics of glass can be improved.
Contrasted can be seen by embodiment 3 and embodiment 4 and embodiment 5, use amino-type silane coupling agent, its coupling effect wants excellent in the coupling effect of medium-sized silane coupling agent, specifically, use two amino-type silane coupling agent, the better excellence of its coupling effect, is more conducive to improving composite materials property.
In addition, can see from embodiment 6 and comparative example 4 contrast, when coupling agent consumption is excessive, the comprehensive mechanical property of matrix material is in a slight decrease on the contrary.This is because what really play action of coupling agents in GFABS matrix material is the unimolecular layer that coupling agent molecule is formed at fiberglass surfacing, therefore too much interpolation coupling agent is unnecessary.When coupling agent consumption is less, along with the increase of consumption, tensile strength and shock strength can be improved to some extent; When the consumption of coupling agent is excessive, this excessive interpolation is unnecessary, and can cause negative impact to the performance of material, causes the performance of material to occur declining.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, and those of ordinary skill in the art can change above-described embodiment within the scope of the invention, revises, replace and modification.
Claims (10)
1. a high-performance fiber glass reinforced ABS composition, is characterized in that: by weight percentage, comprises following component: ABS resin: 62.4-84.4%, glass fibre: 10-30%, compatilizer: 1-5%, coupling agent: 0.1-1%, auxiliary agent 0.1-3%.
2. high-performance fiber glass reinforced ABS composition according to claim 1, it is characterized in that: described compatilizer is the ABS blend of maleic anhydride graft, percentage of grafting is 1-12%, and its melting means is 1-5g/10min.
3. high-performance fiber glass reinforced ABS composition according to claim 2, it is characterized in that: described ABS resin is vinyl cyanide, divinyl, cinnamic terpolymer, wherein the weight percent content of divinyl is 10-55%, the weight percent content of vinyl cyanide is 15-32%, and cinnamic weight percent content is 30-70%.
4. the high-performance fiber glass reinforced ABS composition according to any one of claim 1-3, is characterized in that: the preparation method of described ABS resin is substance law or emulsion method.
5. high-performance fiber glass reinforced ABS composition according to claim 4, is characterized in that: described glass fibre is the mixing of one or more of long glass fibres or short glass fiber; Preferably, described long glass fibres is alkali free glass fibre, and diameter is 10-16 μm; Preferably, the length of described short glass fiber is 0.2-10mm, and diameter is 8-20 μm.
6. high-performance fiber glass reinforced ABS composition according to claim 1, it is characterized in that: described coupling agent is silane coupling agent, general formula is YSiX3, in formula, Y is non-hydrolytic group, representative and polymer molecule have the active function groups of avidity or response capacity, and preferably, Y is oxygen base, sulfydryl, vinyl, epoxy group(ing), amide group or aminopropyl; X represents the alkoxyl group that can be hydrolyzed, and preferably, X is halogen, alkoxyl group or acyloxy.
7. high-performance fiber glass reinforced ABS composition according to claim 6, is characterized in that: described silane coupling agent is amino-type silane coupling agent, preferably, the number of amino groups that described amino-type silane coupling agent contains is more than 2 or 2.
8. high-performance fiber glass reinforced ABS composition according to claim 1, is characterized in that: described auxiliary agent is the mixing of one or more in thermo-stabilizer, photostabilizer, processing aid, toner or pigment; Preferably, described thermo-stabilizer is selected from more than one in phenols, phosphorous acid esters, monothioester class; Preferably, described photostabilizer is hindered amines or UV light absorber; Preferably, described processing aid is more than one in low molecule ester class stearic acid, metallic soap, stearic acid complex ester or amides.
9. a preparation method for the high-performance fiber glass reinforced ABS composite material according to any one of claim 1-8, is characterized in that:
Comprise the steps:
(1) take ABS resin, compatilizer, coupling agent and auxiliary agent by weight percentage and mix 1-3min in high mixer; Mix, obtain Preblend;
(2) Preblend is placed in the main spout of twin screw extruder, adds glass fibre from side spout, melt extrude, granulating and drying, to obtain final product.
10. the preparation method of high-performance fiberglass reinforced AS matrix material according to claim 9, it is characterized in that: described in the condition that melt extrudes be: a district temperature 180-210 DEG C, two district temperature 190-220 DEG C, three district temperature 190-230 DEG C, four district temperature 190-240 DEG C, five district temperature 190-240 DEG C, six district temperature 190-240 DEG C, seven district temperature 190-240 DEG C, eight district temperature 190-240 DEG C, nine district temperature 190-240 DEG C, engine speed 250-600 rev/min; The length-to-diameter ratio of twin screw extruder is 40:1.
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Cited By (6)
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| CN106116182A (en) * | 2016-06-17 | 2016-11-16 | 巨石集团有限公司 | A kind of reinforced ABS and AS plastics glass fiber infiltration agent and its production and use |
| CN106349636A (en) * | 2016-09-21 | 2017-01-25 | 珠海格力电器股份有限公司 | Enhanced ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof |
| CN106700401A (en) * | 2017-01-18 | 2017-05-24 | 安徽朗迪叶轮机械有限公司 | Centrifuging fan blade and preparation method thereof |
| CN112210172A (en) * | 2020-10-13 | 2021-01-12 | 上海金发科技发展有限公司 | Creep-resistant glass fiber reinforced styrene compound and preparation method thereof |
| CN114213799A (en) * | 2021-11-30 | 2022-03-22 | 金发科技股份有限公司 | Heat-resistant ABS composition and preparation method and application thereof |
| CN114591577A (en) * | 2022-03-04 | 2022-06-07 | 武汉金发科技有限公司 | Interface modifier and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106116182A (en) * | 2016-06-17 | 2016-11-16 | 巨石集团有限公司 | A kind of reinforced ABS and AS plastics glass fiber infiltration agent and its production and use |
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| CN106349636A (en) * | 2016-09-21 | 2017-01-25 | 珠海格力电器股份有限公司 | Enhanced ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof |
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| CN112210172A (en) * | 2020-10-13 | 2021-01-12 | 上海金发科技发展有限公司 | Creep-resistant glass fiber reinforced styrene compound and preparation method thereof |
| CN112210172B (en) * | 2020-10-13 | 2023-05-30 | 上海金发科技发展有限公司 | Creep-resistant glass fiber reinforced styrene compound and preparation method thereof |
| CN114213799A (en) * | 2021-11-30 | 2022-03-22 | 金发科技股份有限公司 | Heat-resistant ABS composition and preparation method and application thereof |
| CN114591577A (en) * | 2022-03-04 | 2022-06-07 | 武汉金发科技有限公司 | Interface modifier and preparation method and application thereof |
| CN114591577B (en) * | 2022-03-04 | 2023-09-26 | 武汉金发科技有限公司 | Interface modifier and preparation method and application thereof |
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