CN104845288A - High-toughness glass fiber reinforced polymer alloy and preparation method thereof - Google Patents
High-toughness glass fiber reinforced polymer alloy and preparation method thereof Download PDFInfo
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- CN104845288A CN104845288A CN201510217661.4A CN201510217661A CN104845288A CN 104845288 A CN104845288 A CN 104845288A CN 201510217661 A CN201510217661 A CN 201510217661A CN 104845288 A CN104845288 A CN 104845288A
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Abstract
The invention relates to high-toughness glass fiber reinforced polymer alloy and a preparation method thereof. The alloy comprises components of, by weight, 40 parts to 95 parts of matrix resin, 5 parts to 50 parts of plasma processed glass fiber, 1 part to 10 parts of flexibilizers, 0.1 part to 5 parts of coupling agents, 0.1 part to 1 part of antioxidants and 0.1 part to 1 part of lubricants. According to the preparation method, glass fibers which are not sized are subjected to plasma processing, and accordingly, the roughness and active groups on glass fiber surfaces are increased, and the wettability of the flexibilizer to the glass fibers and the dispersity of the glass fibers in polymers are increased; by the use of the coupling agents, the wettability of the flexibilizer to the glass fibers and the fiber and polymer bonding performance are further improved, and accordingly, the strength of the glass fiber enhancement material is improved greatly, and the glass fiber enhancement polymer alloy material toughness is improved.
Description
Technical field
The invention belongs to macromolecule modified technical field, relate to a kind of high tenacity Glass Fiber Reinforced Polymer Alloy And Preparation Method.
Background technology
Because intensity limits the application of polymkeric substance in certain degree, so it is more and more extensive to strengthen the application of polymer alloy by fiber in recent years.Especially glass fibre has relatively low price and makes the application of glass fibre reinforcement more and more extensive, but although glass fibre reinforced composion has higher rigidity, but adding of glass makes the decline of the toughness of polymer alloy extremely serious, limit Glass Fiber Reinforced Polymer alloy to toughness reguirements high field application, therefore, the improvement of Glass Fiber Reinforced Polymer toughness becomes the problem quite needing to solve.
At present, the main method of toughness reinforcing Glass Fiber Reinforced Polymer alloy is for adding toughner, and toughner is mainly esters of acrylic acid and elastomerics etc., and wherein esters of acrylic acid is mainly MBS.But these toughner toughening effect after certain addition improves unsatisfactory, is therefore necessary to develop the preparation method that a kind of toughness keeps good Glass Fiber Reinforced Polymer alloy.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of high tenacity Glass Fiber Reinforced Polymer Alloy And Preparation Method is provided, matrix resin and the glass fibre after Cement Composite Treated by Plasma are mainly prepared a kind of Glass Fiber Reinforced Polymer alloy of high-intensity high-tenacity by Screw Extrusion by the method, the preparation method of this high tenacity Glass Fiber Reinforced Polymer is mainly through carrying out Cement Composite Treated by Plasma to unsized fiberglass filament, increase the roughness of fiber surface by Cement Composite Treated by Plasma and improve the polar group (as hydroxyl etc.) of fiberglass surfacing, improve the wettability of glass fibre and polymkeric substance, the cohesive strength of fiber and polymkeric substance and toughner is improved further by adding coupling agent, thus greatly improve the toughness of glass fibre reinforcement.
Object of the present invention can be achieved through the following technical solutions:
First aspect, the invention provides a kind of high tenacity Glass Fiber Reinforced Polymer alloy, comprises following component and weight part:
Preferably, described Cement Composite Treated by Plasma glass is that the non-starching continuous glass-fiber of 5 ~ 15 μm is through Cement Composite Treated by Plasma gained by diameter.
Preferably, described unsized continuous glass-fiber rate of weight loss after Cement Composite Treated by Plasma is 0.1 ~ 1.0%.
Preferably, directly import twin screw extruder after described unsized continuous glass-fiber stops 1 ~ 5min in atmosphere after Cement Composite Treated by Plasma and prepare described high tenacity Glass Fiber Reinforced Polymer alloy.
Described plasma treatment specifically refers to that in reactant gas atmosphere be oxygen, nitrogen or ammonia isoreactivity gas, the weight fraction of loss after regulating glass fibre to be etched by the air pressure adjusted in the discharge power of plasma reactor and plasma reactor, make the weight fraction of etching remain on 0.1 ~ 1.0%, after then allowing the long filament handled well stop 1 ~ 5min in atmosphere, directly import twin screw extruder; For avoiding the performance of glass overetch damaged material, the rate of weight loss of glass is 0.1 ~ 1.0%; The parameters such as the pulse in plasma reactor, two step voltages and treatment time are regulated and controled by rate of weight loss.
Preferably, described matrix resin comprises one or both and the two or more mixture in bisphenol A polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polymeric amide, ABS resin.
Preferably, described toughner is noncrosslinking toughner, comprises the non-reacted toughner of non-crosslinked or the agent of non-crosslinked reactive toughening; The non-reacted toughner of described non-crosslinked comprises EMA, EBA, EPDM, thermoplastic styrene elastomer; The agent of described non-crosslinked reactive toughening comprises EMA-g-MAH, EMA-g-GMA, EBA-g-MAH, EBA-g-GMA or thermoplastic styrene elastomer grafting active function groups.
Preferably, described coupling agent comprises silane coupling agent, and wherein, the general formula of silane coupling agent is RSiX3, and in formula, R represents the groups such as amino, sulfydryl, vinyl, epoxy group(ing), cyano group or methacryloxy; Silane coupling agent is in fact the silane that a class has organo-functional group, have in the molecule thereof simultaneously can and inanimate matter material (as glass, silica sand, metal etc.) chemically combined reactive group and with organic material (synthetic resins etc.) chemically combined reactive group; These groups and different matrix resins all have stronger response capacity, and X represents the alkoxyl group (as methoxyl group, oxyethyl group etc.) that can be hydrolyzed.
Preferably, described oxidation inhibitor comprises one or more in commercially available oxidation inhibitor 245, irgasfos 168, antioxidant 1010, oxidation inhibitor PEP-8T or S9228.
Preferably, described lubricant comprise in whiteruss, solid paraffin, silane polymer, soap, stearic amide, calcium stearate, Zinic stearas, methylene bis stearic amide or N, N-ethylene bis stearic acid amide, tetramethylolmethane stearic acid one or more.
Second aspect, the invention provides a kind of preparation method of described high tenacity Glass Fiber Reinforced Polymer alloy, specifically comprises the following steps:
Step one, to get the raw materials ready according to following component and weight part: matrix resin 40 ~ 95 parts, Cement Composite Treated by Plasma glass 5 ~ 50 parts, toughner 1 ~ 10 part, coupling agent 0.1 ~ 5 part, 0.1 ~ 1 part, oxidation inhibitor, lubricant 0.1 ~ 1 part;
Step 2, described matrix resin, coupling agent, toughner and oxidation inhibitor and lubricant to be added in mixing and blending machine successively, fully after mixing, derive, then be placed in twin screw extruder; Cement Composite Treated by Plasma glass is fed by rear section side and is added after matrix resin plastifies completely, and the temperature controlling twin screw extruder is 230 ~ 380 DEG C, and rotating speed is 300 ~ 1000r/min, extruding pelletization, obtains described high tenacity Glass Fiber Reinforced Polymer alloy;
Preferably, the screw rod of described twin screw extruder is the length-to-diameter ratio >30 of parallel dual-screw, described twin screw.
Compared with prior art, the present invention has beneficial effect as described below:
1, the glass used is unsized continuous glass fibre, can save starching and the short process costs cut;
2, by carrying out Cement Composite Treated by Plasma to glass, roughness and the active group of fiberglass surfacing can be improved, thus increase glass fibre toughner to the wettability of glass and dispersiveness in the polymer;
3, improving the adhesive property of toughner to the wettability of fiber and fiber and polymkeric substance further by the use of coupling agent, greatly improving the toughness of Glass Fiber Reinforced Polymer alloy material when improving the intensity of Glass Fiber Reinforced Polymer simultaneously.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the application preparation method schematic flow sheet.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
In the present invention, described matrix resin mainly comprises the polymkeric substance containing reactive behavior such as bisphenol A polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate, polymeric amide; Described coupling agent mainly silane coupling agent; Described plasma treatment glass, be that the glass of 5 ~ 15 μm long filament after Cement Composite Treated by Plasma is through screw rod shearing gained by diameter, described plasma treatment specifically refers to that in reactant gas atmosphere be oxygen, nitrogen or ammonia isoreactivity gas, the weight fraction of loss after regulating glass fibre to be etched by the air pressure adjusted in the discharge power of plasma reactor and plasma reactor, make the weight fraction of etching remain on 0.1 ~ 1.0%, after then allowing the long filament handled well stop 1 ~ 5min in atmosphere, directly import twin screw extruder; For avoiding the performance of glass overetch damaged material, the rate of weight loss of glass is 0.1 ~ 1.0%; Other auxiliary agents comprise oxidation inhibitor and lubricant is commercially available; Preparation method as shown in Figure 1.In order to better understand and implement, describe a kind of high tenacity Glass Fiber Reinforced Polymer of the present invention material and preparation method thereof in detail below in conjunction with embodiment.
For p-poly-phenyl dioctyl phthalate butanediol ester.
The following preparation method for high tenacity Glass Fiber Reinforced Polymer alloy of the present invention, specifically comprises the steps:
Step one, to get the raw materials ready by the component in table 1 and weight part:
Step 2, polybutylene terephthalate, toughner, coupling agent, oxidation inhibitor and lubricant to be mixed in mixing and blending machine;
Step 3, the mixture of step 2 is entered twin screw extruder by main spout, glass is by the blended granulation of side spout, and obtained alloy particle, the barrel zone temperature of forcing machine is 260 DEG C, and screw speed is 600rpm.
Described polybutylene terephthalate viscosity is 0.98 ~ 1.02dl/g; Described Cement Composite Treated by Plasma continuous glass-fiber (embodiment 1 ~ 3, comparative example 1) for the diameter after Cement Composite Treated by Plasma be 10 μm of non-starching continuous glass-fibers, the condition of process is: atmosphere is N
2(40%)+Ar (60%), vacuum tightness is 0.6Pa, and power is 240W, and rate of weight loss is 0.5%;
Described plasma body excess processes continuous glass-fiber (comparative example 4) for the diameter after Cement Composite Treated by Plasma be 10 μm of non-starching continuous glass-fibers, the condition of process is: atmosphere is N
2(40%)+Ar (60%), vacuum tightness is 0.6Pa, and power is 240W, and rate of weight loss is 1.5%;
Described chopped glass fiber (comparative example 3) for the diameter after Cement Composite Treated by Plasma be 10 μm, length is the non-starching continuous glass-fiber of 4.5mm, and the condition of process is: atmosphere is N
2(40%)+Ar (60%), vacuum tightness is 0.6Pa, and power is 240W, and rate of weight loss is 0.5%;
Described non-crosslinked toughner is
aX8900;
Described crosslinked toughner is the nucleocapsid structure toughner MBS with certain degree of crosslinking, and model is LG EM500;
Described coupling agent is silane coupling agent, and model is KH570;
Described oxidation inhibitor is two stearyl alcohol pentaerythritol diphosphites;
Described lubricant is the mixing of 0.2 part of whiteruss and 0.1 part of solid paraffin.
Table 1 embodiment 1 ~ 3 and each component of comparative example 1 ~ 4 and content
Below for polyamide 66
Specifically comprise the steps:
Step one, to get the raw materials ready by the component in table 2 and weight part:
Step 2, polyamide 66, toughner, coupling agent, oxidation inhibitor and lubricant to be mixed in mixing and blending machine;
Step 3, the mixture of step 2 is entered twin screw extruder by main spout, glass is by the blended granulation of side spout, and obtained alloy particle, the barrel zone temperature of forcing machine is 260 DEG C, and screw speed is 600rpm.
Described polyamide 66 viscosity is 2.60-2.66dl/g;
Described Cement Composite Treated by Plasma continuous glass-fiber is the diameter after Cement Composite Treated by Plasma is 10 μm of non-starching continuous glass-fibers, and the condition of process is: atmosphere is N
2(40%)+Ar (60%), vacuum tightness is 0.6Pa, and power is 240W, and rate of weight loss is respectively 0.1% (embodiment 4), 0.5% (embodiment 5) and 1% (embodiment 6);
Described chopped glass fiber (comparative example 3) for the diameter after Cement Composite Treated by Plasma be 10 μm, length is the non-starching continuous glass-fiber of 4.5mm, and the condition of process is: atmosphere is N
2(40%)+Ar (60%), vacuum tightness is 0.6Pa, and power is 240W, and rate of weight loss is 0.5%;
Described non-crosslinked toughner be EMA-GMA (
aX8900), EMA-MAH (Lotader 6200) and EMA (Lotryal 28MA07);
Described crosslinked toughner is the nucleocapsid structure toughner MBS with certain degree of crosslinking, and model is LG EM500;
Described coupling agent is silane coupling agent, and model is KH570;
Described oxidation inhibitor is two stearyl alcohol pentaerythritol diphosphites;
Described lubricant is the mixing of 0.2 part of whiteruss and 0.1 part of solid paraffin.
Table 2 embodiment 4 ~ 6 and each component of comparative example 5 ~ 8 and content
performance test
The toughness of material generally represents by impelling strength, therefore embodiment and comparative example is carried out Chalpy impact experiment (ASTM D256,1/8 batten) and flexural strength (ASTM D790).Test result is as shown in table 2.
Table 3 embodiment 1 ~ 3 and comparative example 1 ~ 4 test result
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Chalpy impact D256 | 182J/m | 193J/m | 213J/m | 82J/m | 112J/m | 138J/m | 78J/m |
| Flexural strength D790 | 188 | 185 | 183 | 186 | 186 | 184 | 183 |
Table 4 embodiment 4 ~ 6 and comparative example 5 ~ 8 test result
| Performance | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 |
| Chalpy impact D256 | 189J/m | 197J/m | 202J/m | 128J/m | 98J/m | 152J/m | 94J/m |
| Flexural strength D790 | 235 | 23 | 233 | 237 | 238 | 236 |
From table 3 test result:
Difference between embodiment 2 and comparative example 1 is that this shows that noncrosslinking toughner can better toughness reinforcing plasma body Glass Fiber Reinforced Polymer alloy because the kind difference of toughner causes;
The impelling strength difference be better than between comparative example 2 of embodiment 2 is the impelling strength that Cement Composite Treated by Plasma glass can improve strongthener greatly; But comparative example 4 shows when after plasma treated degree, impelling strength reduces obviously.
Difference between embodiment 2 and comparative example 3 shows directly to use continuous fibre can significantly improve the toughness of material.
Known from table 4 test result: the embodiment of polyamide 66 and comparative example, also can to obtain conclusions.
To sum up, using plasma process continuous glass glass by strengthening in coordinating of coupling agent the toughness that matrix resin can significantly improve material with noncrosslinking toughner, and on the rigidity effects of material almost without impact.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
1. a high tenacity Glass Fiber Reinforced Polymer alloy, is characterized in that, comprises following component and weight part:
Described Cement Composite Treated by Plasma glass is that the non-starching continuous glass-fiber of 5 ~ 15 μm is through Cement Composite Treated by Plasma gained by diameter.
2. high tenacity Glass Fiber Reinforced Polymer alloy according to claim 1, is characterized in that, described non-starching continuous glass-fiber rate of weight loss after Cement Composite Treated by Plasma is 0.1 ~ 1.0%.
3. high tenacity Glass Fiber Reinforced Polymer alloy according to claim 1, it is characterized in that, described matrix resin is the mixture of one or more in bisphenol A polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polymeric amide or ABS resin.
4. high tenacity Glass Fiber Reinforced Polymer alloy according to claim 1, it is characterized in that, described toughner is noncrosslinking toughner, comprises the non-reacted toughner of non-crosslinked or the agent of non-crosslinked reactive toughening.
5. high tenacity Glass Fiber Reinforced Polymer alloy according to claim 1, it is characterized in that, described coupling agent comprises silane coupling agent, wherein, the general formula of silane coupling agent is RSiX3, and in formula, R represents amino, sulfydryl, vinyl, epoxy group(ing), cyano group or methacryloxy; X represents the alkoxyl group that can be hydrolyzed.
6. high tenacity Glass Fiber Reinforced Polymer alloy according to claim 1, is characterized in that, described oxidation inhibitor is one or more in oxidation inhibitor 245, irgasfos 168, antioxidant 1010, oxidation inhibitor PEP-8T, S9228.
7. high tenacity Glass Fiber Reinforced Polymer alloy according to claim 1, it is characterized in that, described lubricant is one or more in whiteruss, solid paraffin, silane polymer, soap, stearic amide, calcium stearate, Zinic stearas, methylene bis stearic amide or N, N-ethylene bis stearic acid amide or tetramethylolmethane stearic acid.
8. a preparation method for high tenacity Glass Fiber Reinforced Polymer alloy according to claim 1, is characterized in that, specifically comprise the following steps:
Step one, to get the raw materials ready according to following component and weight part: matrix resin 40 ~ 95 parts, Cement Composite Treated by Plasma glass 5 ~ 50 parts, toughner 1 ~ 10 part, coupling agent 0.1 ~ 5 part, 0.1 ~ 1 part, oxidation inhibitor, lubricant 0.1 ~ 1 part;
Step 2, described matrix resin, coupling agent, toughner and oxidation inhibitor and lubricant to be added in mixing and blending machine successively, fully after mixing, derive, then be placed in twin screw extruder; Cement Composite Treated by Plasma glass is fed by rear section side and is added after matrix resin plastifies completely, and the temperature controlling twin screw extruder is 230 ~ 380 DEG C, and rotating speed is 300 ~ 1000r/min, extruding pelletization, obtains described high tenacity Glass Fiber Reinforced Polymer alloy.
9. the preparation method of high tenacity Glass Fiber Reinforced Polymer alloy according to claim 8, it is characterized in that, the screw rod of described twin screw extruder is the length-to-diameter ratio >30 of parallel dual-screw, described twin screw.
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| CN115466416A (en) * | 2022-08-26 | 2022-12-13 | 上海金山锦湖日丽塑料有限公司 | Impact-resistant improved glass fiber reinforced PC/ABS alloy material and preparation method thereof |
| CN115466416B (en) * | 2022-08-26 | 2024-04-02 | 上海金山锦湖日丽塑料有限公司 | Impact-resistant improved glass fiber reinforced PC/ABS alloy material and preparation method thereof |
| CN115449203A (en) * | 2022-10-24 | 2022-12-09 | 四川坚卓装配式建筑科技有限公司 | Glass fiber reinforced plastic material and preparation method and application thereof |
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