CN102977361A - Method for preparing glass fiber reinforced nylon 6 by in situ polymerization - Google Patents
Method for preparing glass fiber reinforced nylon 6 by in situ polymerization Download PDFInfo
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- CN102977361A CN102977361A CN2012105790341A CN201210579034A CN102977361A CN 102977361 A CN102977361 A CN 102977361A CN 2012105790341 A CN2012105790341 A CN 2012105790341A CN 201210579034 A CN201210579034 A CN 201210579034A CN 102977361 A CN102977361 A CN 102977361A
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Abstract
The invention relates to a method for preparing glass fiber reinforced nylon 6 by in situ polymerization. The raw materials in parts by weight are as follows: 10-30 parts of short glass fibre, 90-70 parts of caprolactam, 0.1-10 parts of water, 0.1-5 parts of lubricating agent, and 0.05-1 part of antioxidant. The method comprises the following steps: adding the weighed raw materials into a high pressure polymerization reaction kettle with a jacket coil, fastening a feed manhole cover, and vacuumizing and replacing air in the kettle by high purity inertial gas, so that the content of oxygen in the kettle is controlled below 0.005%; firstly, reacting for 1.5-3 hours at 220-270 DEG C; then, relieving pressure in the kettle, and vacuumizing and reacting for 0.5-1.5 hours at 250-260 DEG C and at -0.01--0.08MPa of gage pressure; then, discharging and drawing strips from a discharge valve at the bottom of the kettle, wherein the strips through a water tank enter into a granulator to be diced to obtain the product. Compared with conventional products, the impact strength and tensile strength are improved by above 60%, the glass fiber reinforced nylon 6 is smoother in surface, and the production cost is further lowered.
Description
Technical field
The present invention relates to the method that a kind of in-situ polymerization prepares glass fiber reinforced nylon 6, particularly relate to a kind of take short glass fiber as strongthener, hexanolactam closes monomer as nylon 6/poly, adopts one step of hydrolysis situ aggregation method to prepare the method for glass fiber reinforced nylon 6.
Background technology
Nylon 6(is hereinafter to be referred as PA6) engineering plastics have good mechanical property and electrical property, also have simultaneously wear-resisting, oil resistant, self-lubricating, corrosion-resistant and good advantages such as processing characteristics; But the water-absorbent of PA6 is large, low temperature and dry state poor impact toughness, dimensional stability is not good enough, and its range of application is subject to certain restrictions.For adapting to the particular requirement of different field, need to carry out modification to PA 6, especially how to obtain integrating the enhancing toughness-increasing modified material of high rigidity, high strength and high tenacity, especially the target that always lays siege to of people.
Glass fibre has higher cost performance, comprises the characteristics such as dimensional stability, erosion resistance, thermotolerance and easy processing, and therefore, glass fibre is that people are used for the first-selection that the PA6 resin strengthens framework material always.It is a kind of important channel of PA6 modification that glass fibre strengthens, and compares with the PA6 that does not strengthen, and strengthens back draft intensity, flexural strength, hardness, creep resistance, heat-drawn wire and resistance to fatigue etc. and all is largely increased.Since at first the suitability for industrialized production glass fibre strengthened PA, through popularization, the application of the sixties in last century, since the seventies, the output straight line rose from U.S. fiberfil company in 1956.
Traditional glass fibre strengthens among the preparation method of PA6, and can be divided into by used glass fibre length: short glass fiber, long glass fibres are by twin screw extruder and two kinds of methods of PA6 melt blending extruding pelletization; Press the distribution length of glass fibre in the PA6 matrix, glass fibre strengthens PA6 and is divided into chopped glass fiber enhancing PA6 and the long fiberglass reinforced PA 6 of cutting.The long preparation method who cuts fiberglass reinforced PA 6 is that PA6 passes through first the twin screw extruder melting, is then flowed out by extruder die head and adopts particular form and long glass fibres fully to flood, again cooling and dicing; therefore; as long as pelletizing machine knife spacing determines that particle how long, how long Length of Glass Fiber just has.
When adopting traditional twin screw extruder to prepare glass fibre enhancing PA6, because glass fibre shortens at high strength screw rod shearing power effect down cut, the about 0.2-0.4 μ of mean fibre length in gained matrix material m, so short staple length has limited the raising of finished product performances, and especially the goods shock strength significantly reduces; Although adopting rubber modified resin is that base material can improve its shock strength, therefore the rigidity of material can reduce, and both can not take into account, and its application also is restricted thus.
The long roughly the same phase ratio of glass fiber reinforced thermoplastics composite and its short glass fiber of cutting, has better comprehensive physical property, abradability and the better surface luster property high, lower such as physical strength, particularly the intensity of material, rigidity, anti-creep sex change and resistance to fatigue etc. all improve to some extent when glass fibre length is crossed 6.35mm.But the method is to adopt twin screw extruder and certain moduli head linking device on the one hand, and the granulation course of processing is complicated; On the other hand, the method is the same with traditional double-screw extruding pelletizing, also must make the polymer PA6 secondary degradation of polymerization, and mechanical property reduces, and has reduced the use properties of material.
So far, the technology of extruding preparation fiberglass reinforced PA 6 by reaction has CN1554528 and two patents of 101735449A, the method that these two patents adopt all is after at first caprolactam monomer and catalyst mix polymerization being finished, the PA6 polymer is introduced double screw rod extruder, add glass fibre in the double screw rod extruder second half section and react and extrude enhancing modified, finish simultaneously to vacuumize removing the complete caprolactam monomer of unreacted.These two patented technologies all are to extrude just mixing with glass behind the caprolactam polymerization first, therefore, and on the one hand, owing to the polymeric molecular weight of PA6 causes it can not fully mix with glass greatly, effect of impregnation may to glass is poor, and glass leaks outside easily, thereby can make product surface coarse; On the other hand, because polymer and glass also need be extruded through twin screw extruder, inevitable the shredding under the high shear of screw rod of glass shortens, thereby reduces the reinforced effects of glass.
Summary of the invention
In order to overcome existing preparation fiberglass reinforced PA 6 technical deficiencies, invented the method that a kind of in-situ polymerization prepares glass fiber reinforced nylon 6.
In-situ polymerization among the present invention prepares the method for glass fiber reinforced nylon 6 to be implemented according to the following steps: 1) short glass fiber 10～30 parts of (weight fraction, as follows), 90～70 parts of hexanolactams, 0.1～10 part in water, 0.1～5 part of lubricant, 0.05～1 part of antioxidant; 2) will join by each material that above-mentioned prescription weighs up in the high pressure polymerisation reactor with the chuck coil pipe, cover tightly reinforced manhole plate, vacuumize and with air in the high purity inert gas displacement still, make as far as possible that oxygen content is controlled at below 0.005% in the still; 3) heat up: first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; 4) then unsnatch the still internal pressure, at 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; 5) again by reactor bottom bleeder valve discharging drawstring, band namely obtains product of the present invention through entering the dicing machine pelletizing behind the tank.
Short glass fiber among the present invention can be that process or not treated commercially available E type alkali-free or middle alkali short glass fiber through silane coupling agent on the surface, and length can be between 0.5～1.0cm.
Hexanolactam among the present invention can be commercially available industrial polymerization-grade product, and purity is more than 90%.
Water among the present invention can be industrial production with tap water or deionized water.
Lubricant among the present invention can be long carbochain carboxylic acid such as stearic acid, palmitinic acid, montanic acid; Amide waxe such as ethylene bis stearamide, erucicamide; Carboxylic metallic salt such as Zinic stearas, calcium stearate, montanic acid sodium salt, calcium salt.
Antioxidant among the present invention can be hindered phenol compound such as antioxidant 1010, antioxidant 1098, oxidation inhibitor 1035, oxidation inhibitor 1093, oxidation inhibitor 1222, antioxidant 1076; Also can be hindered amine compound such as oxidation inhibitor DNP, oxidation inhibitor H, oxidation inhibitor 4010 or phosphorous acid ester: such as irgasfos 168; Above-mentioned three class antioxidants can be used separately or in twos.
Rare gas element among the present invention can be the high pure nitrogen of nitrogen content 99.999%, also can be the high-purity carbon dioxide of carbonated 99.999%.
High pressure polymerisation reactor of the present invention is with stirring.
The present invention has following effect
Glass fiber reinforced nylon 6 by the present invention's preparation is compared with at present traditional glass fiber reinforced nylon 6, in the situation of same glass fibre content, has following effect:
1, nylon 6 macromolecular materials need be through the thermal process that is subjected to of secondary processing, and the matrix material comprehensive mechanical property is more excellent, and particularly shock strength, tensile strength all improve more than 60%.
2, glass fibre is combined better with the Nylon 6 matrix, and composite material surface is more smooth.
3, simplified production process: saved nylon 6 extraction process and twin screw extruder operation, reduced production cost.
Embodiment
Embodiment 1:To with adding 90.0 parts of hexanolactams, 10.0 parts of short glass fibers, 0.2 part in water, 0.1 part of lubricant stearic acid, 0.05 part in 1010 oxidation inhibitor in the high pressure polymerisation reactor of chuck coil pipe and stirring, cover tightly reinforced manhole plate, vacuumize and with air in the high pure nitrogen displacement still, make as far as possible that oxygen content is controlled at below 0.005% in the still; Then heat up, first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; Again release and 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; React complete, polymer enters the dicing machine pelletizing behind bleeder valve discharging drawstring, the band process tank bottom reactor, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
Embodiment 2:With embodiment 1 to adding 80.0 parts of hexanolactams, 20.0 parts of short glass fibers, 5 parts in water, 2.5 parts of lubricant stearic acids, 0.5 part in 1010 oxidation inhibitor in the high pressure polymerisation reactor of chuck coil pipe and stirring, cover tightly reinforced manhole plate, vacuumize and with air in the high pure nitrogen displacement still, make as far as possible that oxygen content is controlled at below 0.005% in the still; Then heat up, first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; Again release and 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; React complete, polymer enters the dicing machine pelletizing behind bleeder valve discharging drawstring, the band process tank bottom reactor, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
Embodiment 3: with embodiment 1 to adding 70.0 parts of hexanolactams, 30.0 parts of short glass fibers, 10 parts in water, 5 parts of lubricant stearic acids, 1 part in 1010 oxidation inhibitor in the high pressure polymerisation reactor of chuck coil pipe and stirring, cover tightly reinforced manhole plate, vacuumize and with air in the high pure nitrogen displacement still, make as far as possible that oxygen content is controlled at below 0.005% in the still; Then heat up, first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; Again release and 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; React complete, polymer enters the dicing machine pelletizing behind bleeder valve discharging drawstring, the band process tank bottom reactor, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
Embodiment 4:With embodiment 1 to adding 90.0 parts of hexanolactams, 10.0 parts of short glass fibers, 0.1 part in water, 0.1 part of ethylene bis stearamide, 0.05 part in 1098 oxidation inhibitor in the high pressure polymerisation reactor of chuck coil pipe and stirring, cover tightly reinforced manhole plate, vacuumize and with air in the high pure nitrogen displacement still, make as far as possible that oxygen content is controlled at below 0.005% in the still; Then heat up, first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; Again release and 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; React complete, polymer enters the dicing machine pelletizing behind bleeder valve discharging drawstring, the band process tank bottom reactor, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
Embodiment 5:With embodiment 1 to adding 80.0 parts of hexanolactams, 20.0 parts of short glass fibers, 5 parts in water, 2.5 parts of ethylene bis stearamides, 0.5 part in 1098 oxidation inhibitor in the high pressure polymerisation reactor of chuck coil pipe and stirring, cover tightly reinforced manhole plate, vacuumize and with air in the high pure nitrogen displacement still, make as far as possible that oxygen content is controlled at below 0.005% in the still; Then heat up, first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; Again release and 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; React complete, polymer enters the dicing machine pelletizing behind bleeder valve discharging drawstring, the band process tank bottom reactor, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
Embodiment 6: with embodiment 1 to adding 70.0 parts of hexanolactams, 30.0 parts of short glass fibers, 10 parts in water, 5 parts of ethylene bis stearamides, 1 part in 1098 oxidation inhibitor in the high pressure polymerisation reactor of chuck coil pipe and stirring, cover tightly reinforced manhole plate, vacuumize and with air in the high pure nitrogen displacement still, make as far as possible that oxygen content is controlled at below 0.005% in the still; Then heat up, first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; Again release and 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; React complete, polymer enters the dicing machine pelletizing behind bleeder valve discharging drawstring, the band process tank bottom reactor, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
Embodiment 7:With embodiment 1 to adding 0.05 part of 90.0 parts of hexanolactam, 10.0 parts of short glass fibers, 0.1 part in water, 0.1 part in montanic acid sodium, oxidation inhibitor DNP0.05 part, 168 oxidation inhibitor in the high pressure polymerisation reactor of chuck coil pipe and stirring, cover tightly reinforced manhole plate, vacuumize and with air in the high pure nitrogen displacement still, make as far as possible that oxygen content is controlled at below 0.005% in the still; Then heat up, first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; Again release and 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; React complete, polymer enters pelletizing behind bleeder valve discharging drawstring, the band process tank bottom reactor, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
Embodiment 8:With embodiment 1 to adding 0.25 part of 80.0 parts of hexanolactam, 20.0 parts of short glass fibers, 5 parts in water, 2.5 parts in montanic acid sodium, oxidation inhibitor DNP0.25 part, 168 oxidation inhibitor in the high pressure polymerisation reactor of chuck coil pipe and stirring, cover tightly reinforced manhole plate, vacuumize and with air in the high pure nitrogen displacement still, make as far as possible that oxygen content is controlled at below 0.005% in the still; Then heat up, first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; Again release and 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; React complete, polymer enters the dicing machine pelletizing behind bleeder valve discharging drawstring, the band process tank bottom reactor, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
Embodiment 9: with embodiment 1 to adding 0.5 part of 70.0 parts of hexanolactam, 30.0 parts of short glass fibers, 10 parts in water, 5 parts in montanic acid sodium, oxidation inhibitor DNP0.5 part, 168 oxidation inhibitor in the high pressure polymerisation reactor of chuck coil pipe and stirring, cover tightly reinforced manhole plate, vacuumize and with air in the high pure nitrogen displacement still, make as far as possible that oxygen content is controlled at below 0.005% in the still; Then heat up, first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; Again release and 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; React complete, polymer enters the dicing machine pelletizing behind bleeder valve discharging drawstring, the band process tank bottom reactor, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
The comparative example 10:90 parts of relative viscosities are 0.5 part of 2.7 nylon 6,10 parts of short glass fibers, 0.1 part of KH550 coupling agent, 2.5 parts in montanic acid sodium, oxidation inhibitor DNP0.5 part, 168 oxidation inhibitor, mix with high speed mixer, adopt that length-to-diameter ratio is 35, screw extrusion press extruding pelletization on the Ф 30, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
The comparative example 11: 80 parts of relative viscosities are 0.5 part of 2.7 nylon 6,20 parts of short glass fibers, 0.1 part of KH550 coupling agent, 2.5 parts in montanic acid sodium, oxidation inhibitor DNP0.5 part, 168 oxidation inhibitor, mix with high speed mixer, adopt that length-to-diameter ratio is 35, screw extrusion press extruding pelletization on the Ф 30, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
The comparative example 12:70 parts of relative viscosities are 0.5 part of 2.7 nylon 6,30 parts of short glass fibers, 0.1 part of KH550 coupling agent, 2.5 parts in montanic acid sodium, oxidation inhibitor DNP0.5 part, 168 oxidation inhibitor, mix with high speed mixer, adopt that length-to-diameter ratio is 35, screw extrusion press extruding pelletization on the Ф 30, pellet with injector sample preparation detects mechanical property, performance such as table 1 in 100 ℃ of dryings after 4 hours with a conventional oven.
The contrast of table 1 properties of sample
Embodiment of the present invention only is the description that preferred implementation of the present invention is carried out; be not that design of the present invention and scope are limited; under the prerequisite that does not break away from design philosophy of the present invention; engineering technical personnel make technical scheme of the present invention in this area various modification and improvement; all should fall into protection scope of the present invention; the technology contents that the present invention asks for protection all is documented in claims.
Claims (10)
1. an in-situ polymerization prepares the method for glass fiber reinforced nylon 6, and each raw material consists of by weight: 10～30 parts of short glass fibers, 90～70 parts of hexanolactams, 0.1～10 part in water, 0.1～5 part of lubricant, 0.05～1 part of antioxidant; To join according to each material that above-mentioned composition weighs up in the high pressure polymerisation reactor with the chuck coil pipe, cover tightly reinforced manhole plate, vacuumize and with air in the high purity inert gas displacement still, make that oxygen content is controlled at below 0.005% in the still; Heat up: first 220 ℃～270 ℃, confined reaction with pressure 1.5 hours～3 hours; Then unsnatch the still internal pressure, at 250 ℃～260 ℃, gauge pressure-0.01～-vacuumize reaction 0.5 hour～1.5 hours under the 0.08MPa; By reactor bottom bleeder valve discharging drawstring, band obtains product through entering the dicing machine pelletizing behind the tank again.
2. in-situ polymerization according to claim 1 prepares the method for glass fiber reinforced nylon 6, it is characterized in that described short glass fiber is that process or not treated commercially available E type alkali-free or middle alkali short glass fiber through silane coupling agent on the surface, length is between 0.5～1.0cm.
3. in-situ polymerization according to claim 1 prepares the method for glass fiber reinforced nylon 6, it is characterized in that described hexanolactam is commercially available industrial polymerization-grade product, and purity is more than 90%.
4. in-situ polymerization according to claim 1 prepares the method for glass fiber reinforced nylon 6, it is characterized in that described water is industrial production with tap water or deionized water.
5. in-situ polymerization according to claim 1 prepares the method for glass fiber reinforced nylon 6, it is characterized in that described lubricant is long carbochain carboxylic acid or amide waxe.
6. in-situ polymerization according to claim 1 prepares the method for glass fiber reinforced nylon 6, it is characterized in that described antioxidant is hindered phenol compound, hindered amine compound, phosphorous acid ester, above-mentioned three class antioxidants can be used separately or in twos.
7. in-situ polymerization according to claim 5 prepares the method for glass fiber enhanced nylon 5, it is characterized in that described long carbochain carboxylic acid is stearic acid, palmitinic acid, montanic acid; Amide waxe is ethylene bis stearamide, erucicamide; Carboxylic metallic salt such as Zinic stearas, calcium stearate, montanic acid sodium salt, calcium salt.
8. in-situ polymerization according to claim 6 prepares the method for glass fiber reinforced nylon 6, it is characterized in that described hindered phenol compound is antioxidant 1010, antioxidant 1098, oxidation inhibitor 1035, oxidation inhibitor 1093, oxidation inhibitor 1222, antioxidant 1076; Hindered amine compound is oxidation inhibitor DNP, oxidation inhibitor H, oxidation inhibitor 4010; Phosphorous acid ester is irgasfos 168.
9. an in-situ polymerization prepares the method for glass fiber reinforced nylon 6, it is characterized in that described rare gas element is the high pure nitrogen of a nitrogen content 99.999% or the high-purity carbon dioxide of carbonated 99.999%.
10. an in-situ polymerization prepares the method for glass fiber reinforced nylon 6, it is characterized in that described high pressure polymerisation reactor is with stirring.
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| CN2012105790341A CN102977361A (en) | 2012-12-28 | 2012-12-28 | Method for preparing glass fiber reinforced nylon 6 by in situ polymerization |
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| CN2012105790341A CN102977361A (en) | 2012-12-28 | 2012-12-28 | Method for preparing glass fiber reinforced nylon 6 by in situ polymerization |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923312A (en) * | 2014-04-02 | 2014-07-16 | 合肥杰事杰新材料股份有限公司 | High-strength and low-retraction casting nylon composite material and preparation method thereof |
| CN113929936A (en) * | 2021-11-24 | 2022-01-14 | 四川朗迪新材料有限公司 | Glass fiber reinforced in-situ polymerization flame-retardant nylon one-step forming processing method |
| CN115368593A (en) * | 2021-05-19 | 2022-11-22 | 中国石油化工股份有限公司 | Synthetic method of glass fiber reinforced MXD6 |
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| JPS61228036A (en) * | 1985-04-02 | 1986-10-11 | Toyota Central Res & Dev Lab Inc | Glass fiber reinforced resin material |
| CN1251372A (en) * | 1998-10-19 | 2000-04-26 | 谷春茂 | Method for producing miniature vehicle body |
| CN101235197A (en) * | 2007-02-01 | 2008-08-06 | 上海化工研究院天地科技发展有限公司 | Plasticizing modifying treatment method for mould nylon |
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Patent Citations (3)
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| JPS61228036A (en) * | 1985-04-02 | 1986-10-11 | Toyota Central Res & Dev Lab Inc | Glass fiber reinforced resin material |
| CN1251372A (en) * | 1998-10-19 | 2000-04-26 | 谷春茂 | Method for producing miniature vehicle body |
| CN101235197A (en) * | 2007-02-01 | 2008-08-06 | 上海化工研究院天地科技发展有限公司 | Plasticizing modifying treatment method for mould nylon |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923312A (en) * | 2014-04-02 | 2014-07-16 | 合肥杰事杰新材料股份有限公司 | High-strength and low-retraction casting nylon composite material and preparation method thereof |
| CN115368593A (en) * | 2021-05-19 | 2022-11-22 | 中国石油化工股份有限公司 | Synthetic method of glass fiber reinforced MXD6 |
| CN113929936A (en) * | 2021-11-24 | 2022-01-14 | 四川朗迪新材料有限公司 | Glass fiber reinforced in-situ polymerization flame-retardant nylon one-step forming processing method |
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