CN100590145C - Preparation method and composite material of high mechanical performance halogen-free flame-retardant PBT composite material - Google Patents

Preparation method and composite material of high mechanical performance halogen-free flame-retardant PBT composite material Download PDF

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CN100590145C
CN100590145C CN200810089638A CN200810089638A CN100590145C CN 100590145 C CN100590145 C CN 100590145C CN 200810089638 A CN200810089638 A CN 200810089638A CN 200810089638 A CN200810089638 A CN 200810089638A CN 100590145 C CN100590145 C CN 100590145C
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flame retardant
halogen
composite material
retardant
hypophosphite
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CN101260226A (en
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卢文生
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Liu Chengzhi
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Abstract

The invention discloses a preparation method of a high-mechanical-property halogen-free flame-retardant PBT (polybutylene terephthalate) composite material, which comprises the following steps of: (1) weighing; (2) mixing; (3) and (3) mixing and extruding. The invention also discloses a composite material prepared by the method, which comprises the following components: PBT, superfine glass fiber, hindered phenol antioxidant, organic phosphite ester, toughening agent, flame retardant A, flame retardant B and lubricant. The invention has the advantages that: the flame retardant property of the halogen-free flame retardant material reaches UL 94V-0 (0.8mm) grade, and the halogen-free flame retardant material has more outstanding mechanical property than the existing halogen-free flame retardant system and is equivalent to the mechanical property of the halogen-containing flame retardant system, so the halogen-containing flame retardant material can completely replace the existing halogen-containing flame retardant product and halogen-free flame retardant product, and the preparation method is simple and easy to operate. The halogen-free flame-retardant PBT composite material with high mechanical property is widely applied to household appliance accessories, electronic product accessories and the like, and is particularly applied to a cooling fan in the IT industry.

Description

The preparation method of high machinery performance halogen-free anti-flaming PBT composite and matrix material
Technical field
The present invention relates to polymer composite and preparation method thereof, be specifically related to a kind of preparation method and matrix material of halogen-free anti-flaming PBT composite of the high-mechanical property that can be used for industries such as the various household appliances that the environmental protection flame retardant requirement arranged of injection moulding, electronic product accessory.
Background technology
In the prior art, make the fire retardant that anti-flaming PBT composite adopted, about 95% is halogen containing flame-retardant, be the brominated flame-retardant of representative with polybromodiphenyl ether and polybrominated biphenyl material particularly, its efficient height, consumption are few, and be little to the performance impact of material, and it is moderate, its usefulness/price can be equal to than non-other fire retardants, so in China's electronic apparatus series products for export, about 70～80% have all adopted the matrix material that contains this based flame retardant.But in recent years, because bromide fire retardant is subjected to the puzzlement of Dioxins problem, use its (bromo-antimony system) fire-retardant polymer composite the time can generate a large amount of flue dust and corrosive gases in thermo-cracking and burning simultaneously, European Union and Japan put into effect in succession that it is forbidden by decree to this based flame retardant of use are produced matrix material at present.European Union has risen on July 1st, 2006 and has implemented in full the ROHS instruction, and the electronic and electrical equipment that this decree requires to throw in European Union must not contain components such as polybromodiphenyl ether, Polybrominated biphenyl; Japan has also put into effect corresponding standard JISC0950, and the SONY-SS-00259 standard that Sony Corporation puts into effect is more strict to the requirement of fire retardant; In the U.S., the use of bromide fire retardant is forbidden in the legislation of indivedual state government.Therefore, above decree and standard have had a strong impact on the outlet that China adopts the electronic and electrical equipment that the matrix material of this component produces, and therefore must greatly develop the development trend that bittern-free flame-proof material could adapt to the world market.In order to promote quality product, cooperate the requirement of international standard, " the electronics and IT products pollution control management way " of Chinese version RoHS is also from formal enforcement on March 1 in 2007.Also occurred bittern-free flame-proof material in the prior art, this fire retardant material can satisfy environmental protection requirement substantially, but problem such as this series products ubiquity manufacturing course complexity, product mechanical property be lower is applied it and is subjected to certain restriction.Therefore study manufacture method of a kind of high machinery performance halogen-free anti-flaming material and products thereof, promptly become present problem demanding prompt solution.
Summary of the invention
The technical problem to be solved in the present invention is, the low problem of bittern-free flame-proof material mechanical property of producing at preparation method of the prior art, but a kind of preparation method of industrialized mass production high machinery performance halogen-free anti-flaming PBT composite is provided.
Second technical problem that the present invention will solve is, at the lower problem of bittern-free flame-proof material mechanical property of the prior art, the high machinery performance halogen-free anti-flaming PBT composite that adopts preceding method to produce is provided, this matrix material is the flame retardant properties excellence not only, and environmental protection, safety, electrical insulation capability excellence.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of preparation method of high machinery performance halogen-free anti-flaming PBT composite is characterized in that, may further comprise the steps:
(1) weighing: take by weighing each feed composition: PBT, beta glass fibre, hindered phenol antioxygen, organophosphite, toughner, fire retardant A, fire retardant B, lubricant respectively according to prescription;
(2) mix: each component is added in the agitation vat in proportion, stir and make its thorough mixing;
(3) mixing extruding: the raw material behind the thorough mixing is added in the forcing machine, carry out twice above melting mixing after, extrude granulation.
Described step (1) is further comprising the steps of:
(11) preparation fire retardant B: after taking by weighing hypophosphite and silane coupling agent, the two is carried out surface treatment, the concrete operations step is:
(a) take by weighing hypophosphite according to prescription, it is ground 1～10h, then oven dry;
(b) hypophosphite after will drying places N 2Atmosphere in, it is carried out pyroprocessing, all be cooled to room temperature repeatedly more than twice or twice, and after finishing pyroprocessing each time;
(c) silane coupling agent is watered on the cooled hypophosphite surface, after stirring fully absorbs it, make fire retardant B.
Described step (1) is further comprising the steps of:
(12) prepare surface treated alkali free glass fibre: after taking by weighing alkali free glass fibre and silane respectively,, stir then with the two mixing.
Described step (11) and (12) no sequencing.
Described step (3), be that the raw material behind the thorough mixing is added in the twin screw extruder, carry out melting mixing, extrude and granulation that the screw diameter of this twin screw extruder is 30～90mm, the ratio of spiro rod length and diameter is set at 36～40, and extrusion temperature is 200～260 ℃.
Step of the present invention (11), owing to having superior especially consistency between the fire retardant B for preparing through surface treatment step and other components in the matrix material, greatly improved interface between each component in conjunction with dynamics, the lifting of the matrix material machinery performance of preparation is had crucial effects.
Step of the present invention (12) before each component being carried out step (2) mixing, with alkali free glass fibre and silane mixture, stirs, and is prepared into surface treated alkali free glass fibre.Other component compatibilities in surface treated glass fibre and the matrix material are stronger, help further strengthening the mechanical property of whole matrix material.
A kind of matrix material that adopts aforementioned high machinery performance halogen-free anti-flaming PBT composite preparation method is characterized in that, it comprises the component of following weight part ratio:
PBT 35～70％；
Beta glass fibre 0～40%;
Hindered phenol antioxygen 0.2～0.5%;
Organophosphite 0.2～0.5%;
Toughner 0.5～5%;
Fire retardant A 5～10%;
Fire retardant B 15～25%;
Lubricant 0.3～1%.
Wherein said hindered phenol antioxygen is four (3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid pentaerythritol ester; Wherein said organophosphite is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; Wherein said toughner is the multipolymer of methyl methacrylate and butyl acrylate; Wherein said fire retardant A is a melamine phosphate, and described fire retardant B is the mixture of surface treated hypophosphite and silane; Wherein said lubricant is a montanin wax; This montanin wax is brown coal cerinic acid-1-methyl isophthalic acid, the blend of 3-glyceryl ester and lipid acid-montanin wax calcium salt.
Wherein, described beta glass fibre can well merge with the PBT in the component through surface treatment, has improved the mechanical property of material effectively; Described hindered phenol antioxygen is a primary antioxidant, and described hindered phenol antioxygen is specially four (3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid pentaerythritol ester; Described organophosphite is an auxiliary antioxidant, and described organophosphite is specially three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.Among the present invention, the adding of oxidation inhibitor can make PBT have good processing stability in the course of processing, avoids color and luster, performance to change.
Wherein, the methyl methacrylate that toughner comprised and the multipolymer of butyl acrylate can well merge with described PBT body material, have strengthened the toughness of matrix material, can promote the mechanical property of material.
Fire retardant A wherein is a melamine phosphate, and fire retardant B is the mixture of surface treated hypophosphite and silane.Hypophosphite and silane will carry out surface treatment before compound, the fire retardant B mixture of Xing Chenging and other components in the composition (especially PBT that content is bigger and beta glass fibre) have better consistency like this, greatly improved interface between each component in conjunction with dynamics, not only effectively raise the flame retardant resistance of whole material, flame retardant rating reaches UL 94 V-0 levels (0.8mm), improve the mechanical property of this material more greatly, effectively solved the low relatively difficult problem of bittern-free flame-proof material mechanical property of the prior art.
Lubricant wherein can promote the fusion of each component, improves the flowability of described matrix material molten mass effectively, reduces the friction between matrix material solution and processor in the course of processing, has good demoulding effect simultaneously, shortens injection cycle.
Beneficial effect of the present invention is: the preparation method of high machinery performance halogen-free anti-flaming PBT composite provided by the present invention, the technology that it is traditional relatively, it has increased the step of in advance the part component being handled, adopt the halogen-free anti-flaming PBT composite mechanical property height of this method preparation, flame retardant properties is good, the lifting of composite property is had decisive action, and preparation technology is simple, operation easily, the constant product quality of preparation.Matrix material provided by the invention, with respect to halogen-free flameproof product of the prior art, not only its flame retardant properties reaches UL 94 V-0 (0.8mm) level, and has more outstanding mechanical property than existing halogen-free flame-retardant system, suitable with the mechanical property of Halogen flame-retardant system, therefore can substitute the matrix material of the fire-retardant and halogen-free flameproof of existing Halogen fully.The present invention can be widely used in the manufacturing of matrix materials such as household electrical appliances accessory, electronic product accessory or product, is specially adapted to make the used radiator fan of IT industry.
Below in conjunction with embodiment, the present invention is described in more detail.
Embodiment
Embodiment 1: a kind of preparation method of high machinery performance halogen-free anti-flaming PBT composite may further comprise the steps:
(1) weighing:, take by weighing each feed composition: PBT, beta glass fibre, hindered phenol antioxygen, organophosphite, toughner, fire retardant A, fire retardant B, lubricant respectively according to wherein filling a prescription referring to table 1;
(11) preparation fire retardant B: after taking by weighing hypophosphite and silane coupling agent, the two is carried out surface treatment, the concrete operations step is:
(a) take by weighing hypophosphite according to prescription, hypophosphite is ground 1～10h, then oven dry;
(b) hypophosphite after will drying places N 2Atmosphere in, it is carried out pyroprocessing, all be cooled to room temperature repeatedly more than twice or twice, and after finishing pyroprocessing each time;
(c) silane coupling agent is watered on the cooled hypophosphite surface, after stirring fully absorbs it, make fire retardant B.
(12) prepare surface treated alkali free glass fibre: after taking by weighing alkali free glass fibre and silane respectively,, stir then with the two mixing.This step (11) and (12) no sequencing.
(2) mix: each component is added in the agitation vat in proportion, stir and make its thorough mixing;
(3) mixing extruding: the raw material behind the thorough mixing is added in the forcing machine, carry out twice above melting mixing after, extrude granulation.In the present embodiment, be that the raw material behind the thorough mixing is added in the twin screw extruder, carry out melting mixing, extrude and granulation; The screw diameter of this twin screw extruder is 30～90mm, and the ratio of spiro rod length and diameter is set at 36～40, and extrusion temperature is 200～260 ℃.
Referring to table 1, a kind of matrix material that adopts aforementioned high machinery performance halogen-free anti-flaming PBT composite preparation method, it comprises following weight part ratio component: PBT 35～70%, beta glass fibre 0～40%; Hindered phenol antioxygen 0.2～0.5%; Organophosphite 0.2～0.5%; Toughner 0.5～5%; Fire retardant A 5～10%; Fire retardant B 15～25%; Lubricant 0.3～1%.
Concrete, in the present embodiment, the CAS NO. of described PBT is 26062-94-2; Described beta glass fibre (CAS NO. is 65997-17-3) is a toughener, and this glass fibre carries out surface treatment with silane, can well merge with the PBT in the component; Described hindered phenol antioxygen is a primary antioxidant, is specially four (3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid pentaerythritol esters (CAS NO. is 6683-19-8); Described toughner is the multipolymer (CAS NO. is 25852-37-3) of methyl methacrylate and butyl acrylate; Described auxiliary antioxidant adopts organophosphite, is specially three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (CAS NO. is 31570-04-4); Described fire retardant A is melamine phosphate (CAS NO. is 218768-84-4); Described fire retardant B is the mixture of hypophosphite (CAS NO. is 6303-21-5) and silane; Described lubricant is a montanin wax, is specially brown coal cerinic acid-1-methyl isophthalic acid, the blend of 3-glyceryl ester (CAS NO. is 73138-44-0) and lipid acid-montanin wax calcium salt (CAS NO. is 68308-22-5).
Preparation method concrete in the present embodiment is: take by weighing each raw material successively in each the ingredients weight parts ratio shown in table 1 the 2nd row; Before mixing, wherein hypophosphite is carried out surface treatment, detailed process is: at first hypophosphite is ground 1～10h, dry then, the hypophosphite after the oven dry is placed the atmosphere of N2, repeated multiple times (minimum should be more than twice, be generally 3～6 times) carry out pyroprocessing, make its surface state that once chapped, silane is watered on the hypophosphite surface after being cooled to room temperature, mix to stir that it is fully absorbed, promptly make fire retardant B; Surface treatment process before alkali free glass fibre mixes is: with alkali free glass fibre and silane mixture, stir, make its abundant, uniform mixing.The two also can carry out simultaneously.
Each component is reached fire retardant B, the alkali free glass fibre for preparing in advance, get in proportion material add stir thorough mixing in the agitation vat after, add again and carry out repeated multiple times in the twin screw extruder (more than twice, be generally 3～6 times) melting mixing, make each component react fusion fully after, extrude, granulation, the screw diameter of twin screw extruder is 30mm, and the ratio of spiro rod length and diameter is set at 36, and extrusion temperature is 200 ℃.
Embodiment 2: the preparation method of the high machinery performance halogen-free anti-flaming PBT composite that present embodiment provides and matrix material, it is identical with embodiment 1 basically, its difference is, the screw diameter of twin screw extruder is 90mm, the ratio of spiro rod length and diameter is set at 40, and extrusion temperature is 260 ℃; The raw material that this matrix material comprises is table 1 the 3rd listed component of row and part by weight.
Embodiment 3: the preparation method of a kind of high machinery performance halogen-free anti-flaming PBT composite that present embodiment provides and matrix material, basically identical with embodiment 1, its difference is, the screw diameter of twin screw extruder is 60mm, the ratio of spiro rod length and diameter is set at 38, and extrusion temperature is 230 ℃; The raw material that this matrix material comprises is table 1 the 4th listed component of row and part by weight.
Table 1
Material name Embodiment 1 (wt%) Embodiment 2 (wt%) Embodiment 3 (wt%)
Polybutylene terepthatlate 37.5 53.7 62.6
Beta glass fibre 33 15 5
Hindered phenol antioxygen 0.2 0.4 0.5
Organophosphite 0.3 0.2 0.5
Fire retardant A: melamine phosphate 9 7 5
Fire retardant B: the mixture of hypophosphite and silane 15 20 25
The multipolymer of methyl methacrylate and butyl acrylate 4 3 1
Montanin wax 1 0.7 0.4
The prepared high machinery performance halogen-free anti-flaming PBT composite sample of above three embodiment is carried out test performance, its result and employing standard see Table 2, itself and the contrast of traditional bromo-antimony flame-retardant system test result are as can be known, the mechanical property of the matrix material that the present invention is prepared is compared with other halogen-free flame-retardant systems with flame retardant effect, not only each parameter of its mechanical property is higher than other halogen-free flame-retardant systems far away, and its flame retardant properties also reaches V-0 (0.8mm) grade, has excellent technique effect.Matrix material provided by the invention is compared with traditional bromo-antimony flame-retardant system, its mechanical property is suitable, and anti-electric arc ability is far above bromo-antimony flame-retardant system, so this composite property reaches the performance requirement to plastic material such as household electrical appliances accessory, electronic product accessory fully, has broad application prospects.
Table 2
Test event Testing standard Embodiment 1 (containing 33% glass) Embodiment 2 (containing 15% glass) Embodiment 3 (containing 5% glass) Bromo-antimony flame retardant products (containing 30% glass) Halogen-free flameproof product (containing 32.9% glass)
Density (g/cm 3) ISO1183 1.60 1.45 1.35 1.68
Vertical forming shrinking percentage (%) LIXIN-EP 0.4 0.6 1 0.4
Parallel molding shrinkage (%) LIXIN-EP 0.2 0.3 0.8 0.2
Tensile strength (Mpa) ISO527 120 90 65 130 103
Elongation at break (%) ISO527 1.7 3 5 2.5 2
Flexural strength ISO178 170 135 95 180 148.4
Modulus in flexure ISO178 10500 8500 4500 10000 7380
Notched Izod impact strength ISO180 9.5 8 4.5 9.5 8.9
Unnotched impact strength ISO180 50 30 12 50
Fusing point ISO3146-C 220-225 220-225 220-225 220-225
Heat-drawn wire (66psi) ISO75-1 220 210 200 220
Heat-drawn wire (264psi) ISO75-2 210 200 140 210
0.8mm flame retardant rating ISO1210/UL9 4 V-0 V-0 V-0 V-0 V-1
1.6mm glowing filament (℃) IEC 695-2-1 960 960 960 960 960
Anti-electric arc (Volt) UL-746A 600 525 500 325 550

Claims (5)

1.一种高机械性能无卤阻燃PBT复合材料的制备方法，其特征在于，包括以下步骤：1. A preparation method of high mechanical performance halogen-free flame-retardant PBT composite material, is characterized in that, comprises the following steps: (1)称量：按照配方分别称取各原料组分：PBT、超细玻璃纤维、受阻酚抗氧剂、有机亚磷酸酯、增韧剂、阻燃剂A、阻燃剂B、润滑剂；(1) Weighing: Weigh each raw material component according to the formula: PBT, ultrafine glass fiber, hindered phenol antioxidant, organic phosphite, toughener, flame retardant A, flame retardant B, lubricant ; 所述配方是以下重量份比例的组分：Described prescription is the component of following weight ratio: PBT             35～70％；PBT 35～70%; 超细玻璃纤维    5～40％；Ultrafine glass fiber 5-40%; 受阻酚抗氧剂    0.2～0.5％；Hindered phenol antioxidant 0.2～0.5%; 有机亚磷酸酯    0.2～0.5％；Organic phosphite 0.2～0.5%; 增韧剂          0.5～5％；Toughener 0.5～5%; 阻燃剂A         5～10％；Flame retardant A 5～10%; 阻燃剂B         15～25％；Flame retardant B 15～25%; 润滑剂          0.3～1％；Lubricant 0.3～1%; (2)混合：将各组分按所述配方比例加入搅拌桶中，搅拌使其充分混合；(2) Mixing: Add each component in the mixing tank according to the formula ratio, and stir to make it fully mixed; (3)混炼挤出：将充分混合后的原料加入挤出机中，进行两次以上熔融混炼后，挤出，造粒；(3) Mixing and extruding: Add the fully mixed raw materials into the extruder, perform more than two times of melting and mixing, extrude, and granulate; 所述的步骤(1)包括以下步骤：Described step (1) comprises the following steps: (11)制备阻燃剂B：在称取次磷酸盐及硅烷偶联剂后，对二者进行表面处理，具体操作步骤为：(11) Prepare flame retardant B: after weighing hypophosphite and silane coupling agent, carry out surface treatment to both, concrete operation steps are: (a)按照配方称取次磷酸盐，将次磷酸盐研磨1～10h，然后烘干；(a) Weigh the hypophosphite according to the formula, grind the hypophosphite for 1 to 10 hours, and then dry it; (b)将烘干后的次磷酸盐置于N2的气氛中，对其进行高温处理，反复两次或两次以上，且每一次完成高温处理后均冷却至室温；(b) placing the dried hypophosphite in an atmosphere of N 2 , subjecting it to high-temperature treatment for two or more times, and cooling to room temperature after each high-temperature treatment; (c)将硅烷偶联剂浇到冷却后的次磷酸盐表面上，搅拌使其充分吸收后，制得阻燃剂B；(c) Pour the silane coupling agent onto the surface of the cooled hypophosphite, stir to make it fully absorbed, and prepare the flame retardant B; (12)制备经过表面处理的无碱玻璃纤维：分别称取无碱玻璃纤维与硅烷后，将二者混合，然后搅拌均匀；(12) Preparation of surface-treated non-alkali glass fiber: after weighing the non-alkali glass fiber and silane respectively, mix the two, and then stir evenly; 所述的步骤(11)与(12)无先后顺序；The steps (11) and (12) are in no sequence; 其中所述的阻燃剂A为三聚氰胺磷酸盐，所述的阻燃剂B为经过表面处理的次磷酸盐与硅烷的复合物；Wherein said flame retardant A is melamine phosphate, and said flame retardant B is a compound of surface-treated hypophosphite and silane; 其中所述的增韧剂为甲基丙烯酸甲酯和丙烯酸丁酯的共聚物；Wherein said toughening agent is a copolymer of methyl methacrylate and butyl acrylate; 其中所述的润滑剂为蒙旦蜡，该蒙旦蜡为褐煤蜡酸-1-甲基-1，3-丙二基酯与脂肪酸-褐煤蜡钙盐的共混物。The lubricant described therein is montan wax, and the montan wax is a blend of montan wax acid-1-methyl-1,3-propanediyl ester and fatty acid-montan wax calcium salt. 2.根据权利要求1所述高机械性能无卤阻燃PBT复合材料的制备方法，其特征在于，所述的步骤(3)，是将充分混合后的原料加入双螺杆挤出机中，进行熔融混炼、挤出并造粒；该双螺杆挤出机的螺杆直径为30～90mm，螺杆长度与直径的比例设定为36～40，挤出温度为200～260℃。2. according to the preparation method of the described high-mechanical performance halogen-free flame-retardant PBT composite material of claim 1, it is characterized in that, described step (3), is to add the fully mixed raw material in the twin-screw extruder, carry out Melting and kneading, extruding and granulating; the screw diameter of the twin-screw extruder is 30-90mm, the ratio of screw length to diameter is set at 36-40, and the extrusion temperature is 200-260°C. 3.一种采用权利要求1所述的高机械性能无卤阻燃PBT复合材料制备方法制得的复合材料，其特征在于，它是以下重量份比例的组分：3. A composite material prepared by the method for preparing a high-mechanical performance halogen-free flame-retardant PBT composite material according to claim 1, characterized in that it is the following components in parts by weight: PBT               35～70％；PBT 35～70%; 超细玻璃纤维      5～40％；Ultrafine glass fiber 5-40%; 受阻酚抗氧剂      0.2～0.5％；Hindered phenol antioxidant 0.2～0.5%; 有机亚磷酸酯      0.2～0.5％；Organic phosphite 0.2～0.5%; 增韧剂            0.5～5％；Toughener 0.5～5%; 阻燃剂A           5～10％；Flame retardant A 5～10%; 阻燃剂B           15～25％；Flame retardant B 15～25%; 润滑剂            0.3～1％；Lubricant 0.3～1%; 其中所述的阻燃剂A为三聚氰胺磷酸盐，所述的阻燃剂B为经过表面处理的次磷酸盐与硅烷的复合物；Wherein said flame retardant A is melamine phosphate, and said flame retardant B is a compound of surface-treated hypophosphite and silane; 其中所述的增韧剂为甲基丙烯酸甲酯和丙烯酸丁酯的共聚物；Wherein said toughening agent is a copolymer of methyl methacrylate and butyl acrylate; 其中所述的润滑剂为蒙旦蜡，该蒙旦蜡为褐煤蜡酸-1-甲基-1，3-丙二基酯与脂肪酸-褐煤蜡钙盐的共混物；The lubricant described therein is montan wax, which is a blend of montan wax acid-1-methyl-1,3-propanediyl ester and fatty acid-montan wax calcium salt; 所述的超细玻璃纤维经过表面处理。The superfine glass fibers are surface treated. 4.根据权利要求3所述的复合材料，其特征在于：其中所述的受阻酚抗氧剂为四(3，5-二叔丁基-4-羟基)苯丙酸季戊四醇酯。4. The composite material according to claim 3, wherein said hindered phenol antioxidant is pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)phenylpropionate. 5.根据权利要求3所述的复合材料，其特征在于：其中所述有机亚磷酸酯为三(2，4-二叔丁基苯基)亚磷酸酯。5. The composite material according to claim 3, wherein the organic phosphite is tris(2,4-di-tert-butylphenyl)phosphite.
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