CN104788622A - Method for grafting modification of polytetrafluoroethylene powder - Google Patents
Method for grafting modification of polytetrafluoroethylene powder Download PDFInfo
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- CN104788622A CN104788622A CN201510248489.9A CN201510248489A CN104788622A CN 104788622 A CN104788622 A CN 104788622A CN 201510248489 A CN201510248489 A CN 201510248489A CN 104788622 A CN104788622 A CN 104788622A
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Abstract
The invention discloses a method for grafting modification of polytetrafluoroethylene powder. According to the method disclosed by the invention, the following raw materials in parts by weight are adopted: 100 parts of polytetrafluoroethylene powder, 100 parts of kerosene, 1-10 parts of a grafting monomer, 0.1-0.5 part of an initiator, 1-10 parts of a free radical stabilizer and 20 parts of anhydrous ethanol; and the method comprises the following steps: firstly putting the polytetrafluoroethylene powder, the kerosene and a grinding medium into a stirring type ball mill for pre-grinding for 0.5-2h at the stirring speed of 500-1000 revolutions/min and at the circulation temperature of below 10 DEG C; then preparing an anhydrous ethanol mixed solution, introducing nitrogen gas for protection, and grinding at the stirring speed of 1500-3000 revolutions/min and at the circulation temperature of -10-20 DEG C to obtain slurry; and finally washing and drying the slurry to obtain a polytetrafluoroethylene powder graft. By adopting the method disclosed by the invention, the surface properties of the polytetrafluoroethylene powder are effectively improved, and the method is applicable to not only the polytetrafluoroethylene powder formed by polymerization, but also the recovered polytetrafluoroethylene powder.
Description
Technical field
The present invention relates to a kind of method of modifying of polytetrafluorethylepowder powder, belong to chemical field.
Background technology
Tetrafluoroethylene has the characteristics such as excellent chemical resistance, thermotolerance, wear resistance, non-viscosity and self lubricity because of it, enjoys the good reputation of " King ", has important purposes in every field.
But because tetrafluoroethylene specific surface energy is lower, poor with the adhesive property of other storeroom, be unfavorable for applying.Therefore, the focus that surface modification is fluorine investigation of materials is always carried out to tetrafluoroethylene.Its method comprises chemic modified method, excimer laser modification, high-energy radiation modification, high-temperature fusion modification and plasma modification etc.High-energy radiation modification is simple to operate, clean, fast, without the need to initiator and catalyzer, percentage of grafting is easy to control, but modified surface loses smooth feeling, and molecular weight sharply declines, and causes mechanical property significantly to decline.Tetrafluoroethylene weathering resistance, the humidity resistance of the process of high-temperature fusion modification method are better, and suitable long-term outdoor uses, and weak point is under high temperature sintering condition, and the dimensional stability of tetrafluoroethylene is poor, not easily keeps shape.Sodium-naphthalene chemistry of complex modification is typical chemical modification method, it is a kind of good method for the treatment of effect in current surface modifying method, but the ptfe surface after process is obviously dimmed or become brownish black, long-term exposure under light illumination adhesive property can significantly decline, need to process a large amount of waste liquid, operational danger is higher.
Summary of the invention
The object of the invention is to the deficiency for existing polytetrafluoroethylmodified modified method, provide a kind of simple, safe graft-modification method for polytetrafluorethylepowder powder.
For achieving the above object, technical scheme of the present invention is: described one
the method of polytetrafluorethylepowder powder graft modification, it is characterized in that:
(1) formula is by weight:
Polytetrafluorethylepowder powder 100
Kerosene 100
Grafted monomer 1 ~ 10
Initiator 0.1 ~ 0.5
Free radical stabilizer 1 ~ 10
Dehydrated alcohol 20
(2) step
1) pre-grinding: the kerosene of the polytetrafluorethylepowder powder of 100 weight parts, 100 weight parts and the grinding medium of 600 weight parts are placed in stirring-type ball mill and carry out wet method pre-grinding, milling time 0.5 ~ 2 hour, stirring velocity 500 ~ 1000 revs/min, ball mill refrigeration cycle temperature controls below 10 DEG C;
2) preparation of dehydrated alcohol mixing solutions: at room temperature, add 1 ~ 10 weight part grafted monomer, 0.1 ~ 0.5 weight part initiator, 1 ~ 10 weight part free radical stabilizer respectively to 20 weight part dehydrated alcohols, after stirring, obtain dehydrated alcohol mixing solutions;
3) graft modification is ground: in the polytetrafluorethylepowder powder kerosene mixed solution after the pre-grinding described in step 1), add step 2) the dehydrated alcohol mixing solutions for preparing, pass into nitrogen as protection gas, stirring velocity 1500 ~ 3000 revs/min, refrigeration cycle temperature controls at-10 DEG C ~ 20 DEG C, grinds and obtains modified polytetrafluoroethylpowder powder slurry after 5 ~ 12 hours;
4) washing and drying: modified polytetrafluoroethylpowder powder slurry step 3) obtained carries out suction filtration, adopts washes of absolute alcohol three times, then dry, obtain polytetrafluorethylepowder powder grafts.
Described polytetrafluorethylepowder powder is the powder of letex polymerization or suspension polymerization, or is the powder of the polyfluortetraethylewastes wastes fragmentation of reclaiming, and its powder diameter is all less than 0.5mm.
Described grafted monomer is the grafted monomer of glycidyl methacrylate, one of maleic anhydride or vinylformic acid, or mixes for above-mentioned two kinds or three kinds of grafted monomer arbitrary proportions.
Described initiator is made up of Oxidizing and Reducing Agents, and the weight ratio of both materials is 1:1, and oxygenant is the compound of hydrogen peroxide, one of Potassium Persulphate or dibenzoyl peroxide, and reductive agent is the compound of triethyl aluminum, one of triethyl-boron or glucose.
Described free radical stabilizer is vinylbenzene, triallyl isocyanurate, N, N ' compound of-phenyl-one of bismaleimides or acrylamide.
Described grinding medium is selected from zirconium white, aluminum oxide, glass sphere or steel ball, and its diameter is 0.1 ~ 3mm.
The colourless transparent liquid that described vinylbenzene adopts 10wt% aqueous sodium hydroxide solution cleaning purification to obtain.
Specifically, technical scheme of the present invention is:
(1) (weight part) is filled a prescription
Polytetrafluorethylepowder powder 100
Kerosene 100
Grafted monomer 1 ~ 10
Initiator 0.1 ~ 0.5
Free radical stabilizer 1 ~ 10
Dehydrated alcohol 20
(2) step
1) pre-grinding: the kerosene of the polytetrafluoroethylene powder of 100 weight parts, 100 weight parts and the grinding medium of 600 weight parts are placed in stirring-type ball mill and carry out wet method pre-grinding, milling time 0.5 ~ 2 hour, stirring velocity 500 ~ 1000 revs/min, ball mill refrigeration cycle temperature controls below 10 DEG C.
2) preparation of dehydrated alcohol mixing solutions: at room temperature, add 1 ~ 10 weight part grafted monomer, 0.1 ~ 0.5 weight part initiator, 1 ~ 10 weight part free radical stabilizer respectively to 20 weight part dehydrated alcohols, after stirring, obtain dehydrated alcohol mixing solutions.
3) graft modification is ground: in the polytetrafluorethylepowder powder kerosene mixed solution after pre-grinding, add step 2) the dehydrated alcohol mixing solutions for preparing; pass into nitrogen as protection gas; stirring velocity 1500 ~ 3000 revs/min; refrigeration cycle temperature controls at-10 ~ 20 DEG C, grinds and obtains modified polytetrafluoroethylpowder powder slurry after 5 ~ 12 hours.
4) washing and drying: modified polytetrafluoroethylpowder powder slurry step 3) obtained carries out suction filtration, adopts washes of absolute alcohol three times, then dry, obtain polytetrafluorethylepowder powder grafts.
In (1) of the present invention, polytetrafluorethylepowder powder is the powder of letex polymerization or suspension polymerization, or is the powder of the polyfluortetraethylewastes wastes fragmentation of reclaiming, and powder diameter is less than 0.5mm.
In (1) of the present invention, grafted monomer is the grafted monomer of glycidyl methacrylate, one of maleic anhydride or vinylformic acid, or mixes for above-mentioned two kinds or three kinds of grafted monomer arbitrary proportions.
In (1) of the present invention, initiator is made up of Oxidizing and Reducing Agents, the ratio of both amount of substances is 1:1, and oxygenant is the compound of hydrogen peroxide, one of Potassium Persulphate or dibenzoyl peroxide, and reductive agent is the compound of triethyl aluminum, one of triethyl-boron or glucose.
In (1) of the present invention, free radical stabilizer is vinylbenzene, triallyl isocyanurate, N, the chemicals of N '-phenyl-one of bismaleimides or acrylamide, be preferably vinylbenzene, the colourless transparent liquid that described vinylbenzene adopts 10wt% aqueous sodium hydroxide solution cleaning purification to obtain.
In (2) of the present invention, grinding medium is selected from zirconium white, aluminum oxide, glass sphere, steel ball etc., and its diameter is 0.1 ~ 3mm.
Beneficial effect of the present invention is: the present invention adopts the ball-milling force principles of chemistry, in inertia tetrafluoroethylene molecular chain grafted polar functional group, effectively improve polytetrafluorethylepowder powder surfactivity, reduce contact angle, improve surface energy, significantly improve the interface adhesion of polytetrafluorethylepowder powder, can add in other materials as properties-correcting agent, such as crystallization nucleation properties-correcting agent, flame-proof modifier and material surface modifying agent, greatly extend the range of application of tetrafluoroethylene, overcome other grafting method and pollute large, to control difficulty and operational hazards shortcoming.This technique has the advantage that flow process is simple, treatment effect good and cost is low, and not easily causes environmental pollution, is applicable to suitability for industrialized production.
Embodiment
Below by way of specific embodiment the present invention be described in more detail or describe, instead of limiting the invention.
Embodiment 1
1 formula
Reclaim polytetrafluorethylepowder powder (0.2 mm) 100 g
Kerosene 100 g
Glycidyl methacrylate 2 g
Hydrogen peroxidase 10 .1 g
Triethyl aluminum 0.33 g
Vinylbenzene 2 g
Dehydrated alcohol 20 g
2 steps
(1) pre-grinding: carry out wet method pre-grinding by 100g polytetrafluorethylepowder powder, 100g kerosene and 600g zirconium white zirconium pearl (diameter 1 mm) are placed in stirring-type ball mill, milling time 1 hour, stirring velocity 800 revs/min, it is 0 DEG C that ball mill refrigeration cycle temperature controls.
(2) preparation of dehydrated alcohol mixing solutions: at room temperature, adds 2g glycidyl methacrylate, 0.1g hydrogen peroxide, 0.3g triethyl aluminum, 2g vinylbenzene respectively to 20g dehydrated alcohol, obtains dehydrated alcohol mixing solutions after stirring.
(3) graft modification is ground: in the polytetrafluorethylepowder powder kerosene mixed solution after pre-grinding, add the dehydrated alcohol mixing solutions prepared by step (2); pass into nitrogen as protection gas; stirring velocity 2000 revs/min; refrigeration cycle temperature controls at-10 DEG C, grinds and obtains modified polytetrafluoroethylpowder powder slurry after 7 hours.
(4) washing and drying: the modified polytetrafluoroethylpowder powder slurry that step (3) obtains is carried out suction filtration, adopts washes of absolute alcohol three times, then dry, obtain polytetrafluorethylepowder powder grafts.Its sample characteristics of for example parameter is as shown in table 1.
Table 1 embodiment 1 is rear polytetrafluorethylepowder powder characteristic before modified
。
Embodiment 2
1 formula
Suspension polymerization polytetrafluorethylepowder powder (20 μm) 100 g
Kerosene 100 g
Glycidyl methacrylate 5 g
Benzoyl peroxide 0.12 g
Triethyl-boron 0.05 g
Vinylbenzene 5 g
Dehydrated alcohol 20 g
2 steps
(1) pre-grinding: carry out wet method pre-grinding by 100g polytetrafluorethylepowder powder, 100g kerosene and 600g alumina bead (diameter 0.2 mm) are placed in stirring-type ball mill, milling time 1 hour, stirring velocity 500 revs/min, it is 10 DEG C that ball mill refrigeration cycle temperature controls.
(2) preparation of dehydrated alcohol mixing solutions: at room temperature, adds 5g glycidyl methacrylate, 0.12g benzoyl peroxide, 0.3g triethyl-boron, 5g vinylbenzene respectively to 20g dehydrated alcohol, obtains dehydrated alcohol mixing solutions after stirring.
(3) graft modification is ground: in the polytetrafluorethylepowder powder kerosene mixed solution after pre-grinding, add the dehydrated alcohol mixing solutions prepared by step (2); pass into nitrogen as protection gas; stirring velocity 3000 revs/min; refrigeration cycle temperature controls at 20 DEG C, grinds and obtains modified polytetrafluoroethylpowder powder slurry after 12 hours.
(4) washing and drying: the modified polytetrafluoroethylpowder powder slurry that step (3) obtains is carried out suction filtration, adopts washes of absolute alcohol three times, then dry, obtain polytetrafluorethylepowder powder grafts.Its sample characteristics of for example parameter is as shown in table 2
Table 2 embodiment 2 is rear polytetrafluorethylepowder powder characteristic before modified
embodiment 3
1 formula (weight part)
Letex polymerization polytetrafluorethylepowder powder (30 μm) 100 g
Kerosene 100 g
Maleic anhydride 10 g
Potassium Persulphate 0.27 g
Glucose 0.18 g
Vinylbenzene 10 g
Dehydrated alcohol 20 g
2 steps
(1) pre-grinding: carry out wet method pre-grinding by the polytetrafluorethylepowder powder of 100g, the kerosene of 100g and 600g steel ball pearl (diameter 0.5 mm) are placed in stirring-type ball mill, milling time 2 hours, stirring velocity 500 revs/min, ball mill refrigeration cycle temperature controls as-10 DEG C.
(2) preparation of dehydrated alcohol mixing solutions: at room temperature, adds 10 g maleic anhydrides, 0.27g Potassium Persulphate, 0.18 g glucose, 10 g vinylbenzene respectively to 20g dehydrated alcohol, obtains dehydrated alcohol mixing solutions after stirring.
(3) graft modification is ground: in the polytetrafluorethylepowder powder kerosene mixed solution after pre-grinding, add the dehydrated alcohol mixing solutions prepared by step (2); pass into nitrogen as protection gas; stirring velocity 1500 revs/min; refrigeration cycle temperature controls at-5 DEG C, grinds and obtains modified polytetrafluoroethylpowder powder slurry after 9 hours.
(4) washing and drying: the modified polytetrafluoroethylpowder powder slurry that step (3) obtains is carried out suction filtration, adopts washes of absolute alcohol three times, then dry, obtain polytetrafluorethylepowder powder grafts.Its sample characteristics of for example parameter is as shown in table 3.
Table 3 embodiment 3 is rear polytetrafluorethylepowder powder characteristic before modified
。
Embodiment 4
1 formula (weight part)
Reclaim polytetrafluorethylepowder powder (100 μm) 100 g
Kerosene 100 g
Vinylformic acid 4 g
Dibenzoyl peroxide 0.24 g
Glucose 0.18 g
Triallyl isocyanurate 4 g
Dehydrated alcohol 20 g
2 steps
(1) pre-grinding: carry out wet method pre-grinding by the polytetrafluorethylepowder powder of 100g, the kerosene of 100g and 600g zirconium white zirconium pearl (diameter 2 mm) are placed in stirring-type ball mill, milling time 1.5 hours, stirring velocity 1000 revs/min, it is 8 DEG C that ball mill refrigeration cycle temperature controls.
(2) preparation of dehydrated alcohol mixing solutions: at room temperature, adds 4 g vinylformic acid, 0.24g dibenzoyl peroxide, 0.18 g glucose, 4 g vinylbenzene respectively to 20g dehydrated alcohol, obtains dehydrated alcohol mixing solutions after stirring.
(3) graft modification is ground: in the polytetrafluorethylepowder powder kerosene mixed solution after pre-grinding, add the dehydrated alcohol mixing solutions prepared by step (2); pass into nitrogen as protection gas; stirring velocity 2000 revs/min; refrigeration cycle temperature controls at 20 DEG C, grinds and obtains modified polytetrafluoroethylpowder powder slurry after 9 hours.
(4) washing and drying: the modified polytetrafluoroethylpowder powder slurry that step (3) obtains is carried out suction filtration, adopts washes of absolute alcohol three times, then dry, obtain polytetrafluorethylepowder powder grafts.Its sample characteristics of for example parameter is as shown in table 4.
Table 4 embodiment 4 is rear polytetrafluorethylepowder powder characteristic before modified
As mentioned above, present invention achieves the graft modification of polytetrafluorethylepowder powder, be not only applicable to the polytetrafluorethylepowder powder be polymerized, and be applicable to the polytetrafluorethylepowder powder of recovery, the contact angle of remarkable reduction and water, improve wetting ability, effectively improve polytetrafluorethylepowder powder surface, reduce powder average particle size, widen the Application Areas of tetrafluoroethylene, this technique is simple simultaneously, treatment effect good and with low cost, not easily causes environmental pollution, is applicable to suitability for industrialized production.
Above-mentioned embodiment is the further description to the present patent application; but the scope of the claims in the present invention protection is not limited to the scope described in embodiment; all employings are equal to the technical scheme of replacement or equivalent deformation, all drop on the protection domain of the claims in the present invention.
Claims (7)
1. a method for polytetrafluorethylepowder powder graft modification, is characterized in that:
(1) formula is by weight:
Polytetrafluorethylepowder powder 100
Kerosene 100
Grafted monomer 1 ~ 10
Initiator 0.1 ~ 0.5
Free radical stabilizer 1 ~ 10
Dehydrated alcohol 20
(2) step
1) pre-grinding: the kerosene of the polytetrafluorethylepowder powder of 100 weight parts, 100 weight parts and the grinding medium of 600 weight parts are placed in stirring-type ball mill and carry out wet method pre-grinding, milling time 0.5 ~ 2 hour, stirring velocity 500 ~ 1000 revs/min, ball mill refrigeration cycle temperature controls below 10 DEG C;
2) preparation of dehydrated alcohol mixing solutions: at room temperature, add 1 ~ 10 weight part grafted monomer, 0.1 ~ 0.5 weight part initiator, 1 ~ 10 weight part free radical stabilizer respectively to 20 weight part dehydrated alcohols, after stirring, obtain dehydrated alcohol mixing solutions;
3) graft modification is ground: in the polytetrafluorethylepowder powder kerosene mixed solution after the pre-grinding described in step 1), add step 2) the dehydrated alcohol mixing solutions for preparing, pass into nitrogen as protection gas, stirring velocity 1500 ~ 3000 revs/min, refrigeration cycle temperature controls at-10 DEG C ~ 20 DEG C, grinds and obtains modified polytetrafluoroethylpowder powder slurry after 5 ~ 12 hours;
4) washing and drying: modified polytetrafluoroethylpowder powder slurry step 3) obtained carries out suction filtration, adopts washes of absolute alcohol three times, then dry, obtain polytetrafluorethylepowder powder grafts.
2. a kind of tetrafluoroethylene graft-modification method according to claim 1, it is characterized in that: described polytetrafluorethylepowder powder is the powder of letex polymerization or suspension polymerization, or be the powder that the polyfluortetraethylewastes wastes reclaimed is broken, its powder diameter is all less than 0.5mm.
3. the method for a kind of polytetrafluorethylepowder powder graft modification according to claim 1 and 2, it is characterized in that: described grafted monomer is the grafted monomer of glycidyl methacrylate, one of maleic anhydride or vinylformic acid, or mix for above-mentioned two kinds or three kinds of grafted monomer arbitrary proportions.
4. the method for a kind of polytetrafluorethylepowder powder graft modification according to claim 1 and 2, it is characterized in that: described initiator is made up of Oxidizing and Reducing Agents, the weight ratio of both materials is 1:1, oxygenant is the compound of hydrogen peroxide, one of Potassium Persulphate or dibenzoyl peroxide, and reductive agent is the compound of triethyl aluminum, one of triethyl-boron or glucose.
5. the method for a kind of polytetrafluorethylepowder powder graft modification according to claim 1 and 2, it is characterized in that: described free radical stabilizer is vinylbenzene, triallyl isocyanurate, N, N ' compound of-phenyl-one of bismaleimides or acrylamide.
6. the method for a kind of polytetrafluorethylepowder powder graft modification according to claim 1 and 2, is characterized in that: described grinding medium is selected from zirconium white, aluminum oxide, glass sphere or steel ball, and its diameter is 0.1 ~ 3mm.
7. the method for a kind of polytetrafluorethylepowder powder graft modification according to claim 3, is characterized in that: the colourless transparent liquid that described vinylbenzene adopts 10wt% aqueous sodium hydroxide solution cleaning purification to obtain.
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| CN201510248489.9A CN104788622A (en) | 2015-05-17 | 2015-05-17 | Method for grafting modification of polytetrafluoroethylene powder |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140324A (en) * | 2015-09-01 | 2015-12-09 | 北京汉能光伏投资有限公司 | Solar cell protective film |
| CN106496427A (en) * | 2016-10-27 | 2017-03-15 | 四川大学 | A kind of method for preparing surface modification ptfe micropowder |
| CN106699979A (en) * | 2016-12-05 | 2017-05-24 | 彭州市运达知识产权服务有限公司 | PTFE-g-MAH modified polymer and preparation method thereof |
| CN108189520A (en) * | 2017-12-28 | 2018-06-22 | 浙江华正新材料股份有限公司 | A kind of production method of modified polytetrafluoroethylcopper copper clad plate |
| CN109280135A (en) * | 2018-08-30 | 2019-01-29 | 铨盛聚碳科技股份有限公司 | A kind of anti-dripping agent and preparation method thereof with superior compatibility |
| CN110724329A (en) * | 2019-11-05 | 2020-01-24 | 中化石化销售有限公司 | High-density polyethylene pipe mixed material and preparation method thereof |
| CN114149541A (en) * | 2021-11-18 | 2022-03-08 | 万华化学（宁波）有限公司 | Acrylic ester and acrylamide grafted polytetrafluoroethylene and high-gloss mirror-surface wear-resistant flame-retardant polycarbonate material |
| CN114437403A (en) * | 2021-12-28 | 2022-05-06 | 浙江宁奇环保材料科技有限公司 | Grafting modification method for regeneration of polytetrafluoroethylene powder |
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| WO2003035724A1 (en) * | 2001-10-24 | 2003-05-01 | Daikin Industries, Ltd. | Ptfe powder and method for producing ptfe powder for molding |
| WO2006095963A1 (en) * | 2005-03-10 | 2006-09-14 | Ji-Ho Park | Suspension particle comprising tetrafluoroethylene polymer and manufacturing method thereof |
| CN101177516A (en) * | 2006-11-10 | 2008-05-14 | 丁永津 | High-wearing polytetrafluoroethylene composite material and method for making same |
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| WO2003035724A1 (en) * | 2001-10-24 | 2003-05-01 | Daikin Industries, Ltd. | Ptfe powder and method for producing ptfe powder for molding |
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| CN101177516A (en) * | 2006-11-10 | 2008-05-14 | 丁永津 | High-wearing polytetrafluoroethylene composite material and method for making same |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140324A (en) * | 2015-09-01 | 2015-12-09 | 北京汉能光伏投资有限公司 | Solar cell protective film |
| CN106496427A (en) * | 2016-10-27 | 2017-03-15 | 四川大学 | A kind of method for preparing surface modification ptfe micropowder |
| CN106699979A (en) * | 2016-12-05 | 2017-05-24 | 彭州市运达知识产权服务有限公司 | PTFE-g-MAH modified polymer and preparation method thereof |
| CN108189520A (en) * | 2017-12-28 | 2018-06-22 | 浙江华正新材料股份有限公司 | A kind of production method of modified polytetrafluoroethylcopper copper clad plate |
| CN108189520B (en) * | 2017-12-28 | 2020-12-01 | 浙江华正新材料股份有限公司 | Manufacturing method of modified polytetrafluoroethylene copper-clad plate |
| CN109280135A (en) * | 2018-08-30 | 2019-01-29 | 铨盛聚碳科技股份有限公司 | A kind of anti-dripping agent and preparation method thereof with superior compatibility |
| CN110724329A (en) * | 2019-11-05 | 2020-01-24 | 中化石化销售有限公司 | High-density polyethylene pipe mixed material and preparation method thereof |
| CN114149541A (en) * | 2021-11-18 | 2022-03-08 | 万华化学（宁波）有限公司 | Acrylic ester and acrylamide grafted polytetrafluoroethylene and high-gloss mirror-surface wear-resistant flame-retardant polycarbonate material |
| CN114149541B (en) * | 2021-11-18 | 2023-09-19 | 万华化学（宁波）有限公司 | Acrylic ester and acrylamide grafted polytetrafluoroethylene and high-optical-surface wear-resistant flame-retardant polycarbonate material |
| CN114437403A (en) * | 2021-12-28 | 2022-05-06 | 浙江宁奇环保材料科技有限公司 | Grafting modification method for regeneration of polytetrafluoroethylene powder |
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Application publication date: 20150722 |