CN103159611B - Preparation method of flame retardant type separant - Google Patents
Preparation method of flame retardant type separant Download PDFInfo
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- CN103159611B CN103159611B CN201110419932.6A CN201110419932A CN103159611B CN 103159611 B CN103159611 B CN 103159611B CN 201110419932 A CN201110419932 A CN 201110419932A CN 103159611 B CN103159611 B CN 103159611B
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Abstract
Aiming at spontaneous combustion caused by improper dispose in storage and transportation of powder rubber, the invention provides a preparation method of a flame retardant type separant. The method is as below: conducting an addition reaction on a halogen donor of carbon tetrachloride and a halogen acceptor of unsaturated fatty acid, and saponifying by a sodium hydroxide aqueous solution, so as to prepare the separant with flame retardant function. The flame retardant type separant can be used in condensation process of rubber latex and preparation of powder rubber product with flame retardance, and can guarantee safety of product storage and transportation process.
Description
Technical field
The present invention relates to a kind of preparation method of functional type separant, specifically a kind of preparation method being applicable to separant prepared by powdered rubber with anti-flaming function.
Background technology
The preparation method of powdered rubber mainly contains mechanical crushing method, spray-drying process and moditying polybrene test etc.Three kinds of methods all need to use separant, and separant effect prevents rubber particles surfaces stick, main point inorganics and the large class of inorganics two, inorganics, as: calcium carbonate, talcum powder, carbon black, white carbon black, water glass etc.; Organism, as: macromolecule resin, divalent soap etc.No matter be inorganic separant or organic separant, in powdered rubber production process, only play the effect that isolation is antiseized, do not retrieve the bibliographical information that separant has flame retardant resistance.
At present, the flame resistant method in niggerhead field mainly contains additional fire retardant and fires blend rubber two kinds of methods with difficulty.Additional fire retardant has inorganic combustion inhibitor and organic fire-retardant, the general tool cooling of inorganic combustion inhibitor and iris action, and common kind has aluminium hydroxide, magnesium hydroxide, boron system thing and molybdenum system thing etc.; Organic fire-retardant is then based on brominated, chlorine or phosphorous organic compound, and brominated flame retardant can discharge hydrogen bromide in burning, serves as a barrier against oxygen.Yu Zhi etc. proposed in " flame retardant rubber simple analysis " (world rubber industry, the 31st volume the 4th phase the 39th page), added 15 parts of Sb in SBR
2o
3with 30 parts of clorafins or 5 parts of Sb
2o
3, 20 parts of clorafin and 25 parts of Al (OH)
3, the good sizing material of flame retardant resistance can be obtained.Li Ang etc. propose in " rubber flame-retarded and fire retardant " (specialty elastomer goods, the 23rd volume the 3rd phase the 25th page), by brominated phosphoric acid ester, aromatic bromide, Sb
2o
3with ammonium chloride 4 kinds of fire retardants and use, join in SBR, the good sizing material of flame retardant effect can be obtained.With 5 ~ 10 parts of dialkyl phenyl organic phosphates, 10 ~ 15 parts of Sb
2o
3with the flame retardant agent of 3 ~ 10 parts of iodine, add in SBR, the sizing material that flame retardant effect is good can be obtained.Difficult combustion rubber more mainly contains the glue kind of halogen, as chloroprene rubber, polyvinyl chloride, epichlorohydrin rubber, chlorosulfonated polyethylene etc.
The shortcoming that inorganic combustion inhibitor has consumption large, organic fire-retardant expense is high again, even if do not consider these factors, additional fire retardant also not easily realizes in the production process of powdered rubber.When powdered rubber is produced, the inorganic combustion inhibitor added is incompatible with latex system, and fire retardant is by Precipitation; And add organic fire-retardant, due to fire retardant system small molecule component, easily separate out from powdered rubber surface, cause the secondary adhesion of powder particle.The characteristic of sizing material itself is sacrificed again to a certain extent when firing blend rubber with other difficulty.
Summary of the invention
The present invention be directed to the problem easily causing spontaneous combustion in powdered rubber storage and transport process, provide a kind of preparation method of flame retardant type separant, the synthesized separant with fire-retardant group uses in emulsion condensation powdering process, separant is evenly coated on the surface of powdered rubber, fire-retardant group is also evenly distributed on powdered rubber particle surface, therefore impart the flame retardant properties that powdered rubber is certain, thus ensure the safety of storage and transport process.
A preparation method for flame retardant type separant, is characterized in that comprising the following steps:
1) be (0.1 ~ 6) with unsaturated fatty acids acid anhydrides according to mol ratio by halogenic donator: the ratio of 1 mixes, stir, add initiator, the mol ratio of initiator and unsaturated fatty acids acid anhydrides is (0 ~ 3): 1, carries out the addition reaction of 0.5 ~ 5 hour at 30 ~ 150 DEG C of temperature;
2) to step 1) reaction solution in add excessive dilute alkaline aqueous solution, regulate the pH value of reaction solution to be greater than 8, stir and make product in 0.1 ~ 2 hour, thus prepare the separant with flame retardant resistance.
Halogenic donator of the present invention is tetracol phenixin, hydrogenchloride, chlorine, hydrogen bromide or bromine etc., adopts the mode advertised that circulates to pass in reactive component when halogenic donator is gas.Described unsaturated fatty acids acid anhydrides, as halogen acceptor, is selected from the olefin(e) acid acid anhydride with saturation ratio scarcely of the different carbon chain lengths such as acrylic anhydride, iso-butylene acid anhydrides, monoene caproic anhydride, monoene lauric anhydride, monoene stearic acid acid anhydride, diene stearic acid acid anhydride or triolefin stearic acid acid anhydride and structure.
Described initiator is benzoyl peroxide ((PhCO
2)
2), dicumyl peroxide, di-isopropylbenzene hydroperoxide or oxygen etc.
Step 2 of the present invention) described in alkali aqueous solution be sodium hydroxide, potassium hydroxide or ammoniacal liquor etc., acid anhydrides after alkali aqueous solution and halogenation carries out reaction and generates flame retardant type separant, separant is monovalent base metal or ammonium salt, there is hydrophilic radical so soluble in water, separant pH value is greater than 8, and the mass concentration of alkali aqueous solution is 2% ~ 30%.
Flame retardant type separant of the present invention can be applicable to the condensation powdering of the latex such as styrene-butadiene latex, nitrile rubber, natural rubber latex, polybutadiene latex, thus preparation has the powdered rubber of anti-flaming function.
The principle of foundation of the present invention is as follows:
①
②[Cl
3C-CH
2-CHCl-(CH
2)
n-CO]
2O+2NaOH→2Cl
3C-CH
2-CHCl-(CH
2)
n-COONa+H
2O
③2[Cl
3C-CH
2-CHCl-(CH
2)
n-COONa]+CaCl
2→[Cl
3C-CH
2-CHCl-(CH
2)
n-COO]
2Ca+2NaCl
1. chemical equation is unsaturated fatty acids acid anhydrides [CH
2=CH-(CH
2)
n-CO]
2o is at initiator (PhCO
2)
2effect under with halogenic donator CCl
4there is addition reaction; 2. reaction is saponification reaction, carries out reacting the halogen-containing fatty acid anhydride 1. generated the function that saponification makes it to have rubber-coated particle in aqueous; 3. reaction is condensation powdering mechanism, and separant hydrophobic end is coated on rubber particles surface, and water-wet side is at Ca
2+hydrophobic side is become, rubber latex breakdown of emulsion thus form powdered rubber particle under effect.
The fire retardant mechanism of the powdered rubber that flame retardant type separant is coated is as follows:
It is very fierce oxidizing reaction that powdered rubber burns under aerobic conditions, is also chain chemical reaction, generates active HO-and to dissociate free radical, Formed hydrogen compound and water when HO-free radical and rubber molecule meet during burning.Under aerobic conditions, hydrocarbon polymer can continue to decompose generation HO-free radical again, thus forms chain reaction, and burning is continued.Stop rubber combustion or make it extinguish and must block oxygen or reduce HO-number of free radical.Flame retardant type separant decomposes discharges halogen gas and hydrogen halide, and halogen can play the effect of certain blocking-up oxygen; Halogenation Hydrogen Energy and HO-free radical reaction generate water and halide-ions, and halide-ions can generate hydrogen halide with hydrocarbon reaction, and hydrogen halide can eliminate HO-free radical further, thus reduce HO-number of free radical, combustionvelocity are slowed down until extinguish.
The invention provides a kind of separant with anti-flaming function, its oxygen index of powder styrene butadiene rubber using this separant to prepare can bring up to 23% ~ 25% by 18% ~ 20%, makes powdered rubber not easily spontaneous combustion in storage and transport process.
Accompanying drawing explanation
Fig. 1 is the structural representation of flame retardant type separant cladding powder rubber of the present invention.
Embodiment
" % (w) " hereinafter described represents mass concentration.
The flame retardant effect evaluation of a kind of flame retardant type separant of the present invention is as follows, get the rubber latex of 500g, add the flame retardant type separant described in 10 ~ 200g, stirring makes it to mix, then 10 ~ 200g flocculation agent is added, condensation temperature is 10 ~ 80 DEG C, and obtaining slurry obtained Surface coating after washing drying has the powdered rubber product with anti-flaming function separant.Characterize its flame retardant effect by test oxygen index, oxygen index test is carried out according to method described in GB 10707-89.
Embodiment 1:
Add 10mol monoene stearic acid acid anhydride and 20mol CCl in the reactor
4be uniformly mixed, add (the PhCO of 0.1mol
2)
2initiator, controlling temperature of reaction is 40 DEG C, and the NaOH solution adding 5% (w) after reaction 60min in reactor regulates the pH value of reaction solution to be 8.5, obtains separant stand-by after stirring 20min.Get the styrene-butadiene latex 500g of 20% (w), add the foregoing separant of 40g, stir and make it to mix, then add 50gCaCl
2condense, controlling condensing field temperature is 40 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 23.5%, difficult combustion.
Comparative example 1:
Add 10mol monoene stearic acid acid anhydride in the reactor, the NaOH solution adding 5% (w) regulates the pH value of reaction solution to be 8.5, obtains separant stand-by after stirring 20min.Get 20% (w) styrene-butadiene latex 500g, add the foregoing separant of 40g, stir and make it to mix, add 50gCaCl
2condense, controlling condensing field temperature is 40 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 18.7%, inflammable.
Embodiment 2:
Add 10mol diene stearic acid acid anhydride and 1molCCl in the reactor
4be uniformly mixed, add (the PhCO of 0.05mol
2)
2for initiator, controlling temperature of reaction is 30 DEG C, and the NaOH solution adding 50% (w) after reaction 30min in reactor regulates the pH value of reaction solution to be 8.5, obtains separant stand-by after stirring 6min.Get 20% (w) styrene-butadiene latex 500g, add the foregoing separant of 10g, stir and make it to mix, add 200g CaCl
2condense, controlling condensing field temperature is 45 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 24.8%, difficult combustion.
Comparative example 2:
Add 10mol diene stearic acid acid anhydride in the reactor, the NaOH solution adding 50% (w) regulates the pH value of reaction solution to be 8.5, obtains separant stand-by after stirring 6min.Get 20% (w) styrene-butadiene latex 500g, add the foregoing separant of 10g, stir and make it to mix, add 200g CaCl
2condense, controlling condensing field temperature is 45 DEG C, and obtain slurry and obtain powdered rubber after washing drying, in this powdered rubber, be mixed into the clorafin fire retardant of 10 mass parts, surveying its oxygen index is 20.1%.
Embodiment 3:
Add 10mol triolefin stearic acid acid anhydride and 60mol CCl in the reactor
4be uniformly mixed, add (the PhCO of 0.3mol
2)
2for initiator, controlling temperature of reaction is 90 DEG C, and the NaOH solution adding 25% (w) after reaction 180min in reactor regulates the pH value of reaction solution to be 8.9, obtains separant stand-by after stirring 120min.Get 20% (w) natural rubber latex 500g, add the foregoing separant of 200g, stir and make it to mix, add 10g CaCl
2condense, controlling condensing field temperature is 55 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 25.8%, difficult combustion.
Comparative example 3:
Add 10mol triolefin stearic acid acid anhydride in the reactor, the NaOH solution adding 25% (w) regulates the pH value of reaction solution to be 8.9, obtains separant stand-by after stirring 120min.Get 20% (w) natural rubber latex 500g, add the foregoing separant of 200g, add 10g clorafin fire retardant, stir and make it to mix, add 10g CaCl
2condense, controlling condensing field temperature is 55 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 20.6%, inflammable.
Embodiment 4:
Add 10mol monoene stearic acid acid anhydride in the reactor, be blown into 10mol HCl stirring and make it mixing, be blown into 20mol O
2for initiator, controlling temperature of reaction is 120 DEG C, and the NaOH solution adding 3% (w) after reaction 30min in reactor regulates the pH value of reaction solution to be 8.6, obtains separant stand-by after stirring 60min.Get 20% (w) nitrile rubber 500g, add the foregoing separant of 50g, stir and make it to mix, add 60gMgCl
2condense, controlling condensing field temperature is 60 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 25.5%, difficult combustion.
Comparative example 4:
Get 20% (w) nitrile rubber 500g, add the commercially available separant sodium stearate of 50g, stir and make it to mix, add 60g MgCl
2condense, controlling condensing field temperature is 60 DEG C, and obtain slurry and obtain powdered rubber after washing drying, add the blended rear sample preparation with it of 0.5g commodity fire retardant tributyl phosphate, surveying its oxygen index is 23.4%, and flame retardant effect is poor.
Embodiment 5:
Add 10mol monoene stearic acid acid anhydride in the reactor, be blown into 30mol HBr stirring and make it mixing, be blown into 15mol O
2for initiator, controlling temperature of reaction is 150 DEG C, and the NaOH solution adding 30% (w) after reaction 240min in reactor regulates the pH value of reaction solution to be 8.3, obtains separant stand-by after stirring 30min.Get 20% (w) butadiene latex 500g, add the foregoing separant of 100g, stir and make it to mix, add 120gCaCl
2condense, controlling condensing field temperature is 80 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 23.8%, difficult combustion.
Comparative example 5:
Get 20% (w) butadiene latex 500g, add the commercially available separant potassium oleate of 100g, stir and make it to mix, add 120g CaCl
2condense, controlling condensing field temperature is 80 DEG C, and obtain slurry and obtain powdered rubber after washing drying, add the blended sample preparation with it of 0.5g commodity fire retardant hexabromocyclododecane, surveying its oxygen index is 20.1%, inflammable.
Embodiment 6:
Add the Br of 10mol monoene stearic acid acid anhydride and 50mol in the reactor
2stirring makes it to mix, and does not add initiator, and controlling temperature of reaction is 150 DEG C, and the NaOH solution adding 5% (w) after reaction 120min in reactor regulates the pH value of reaction solution to be 10, obtains separant stand-by after stirring 120min.Get 20% (w) styrene-butadiene latex 500g, add the foregoing separant of 30g, stir and make it to mix, add 200g MgSO
4condense, controlling condensing field temperature is 10 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 22.9%, difficult combustion.
Comparative example 6:
Get 20% (w) styrene-butadiene latex 500g, add the commercially available separant potassium oleate of 30g, add 0.5g commodity fire retardant tributyl phosphate, stir and make it to mix, add 200g MgSO
4condense, controlling condensing field temperature is 10 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 21.9%, and flame retardant effect is not good.
Embodiment 7:
Add 10mol monoene stearic acid acid anhydride and the Cl being blown into 60mol in the reactor
2stirring makes it to mix, and controlling temperature of reaction is 30 DEG C, and the NaOH solution adding 25% (w) after reaction 300min in reactor regulates the pH value of reaction solution to be 9.5, obtains separant stand-by after stirring 10min.Get 20% (w) styrene-butadiene latex 500g, add the foregoing separant of 200g, stir and make it to mix, add 100g Al
2(SO
4)
3condense, controlling condensing field temperature is 80 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 22.7%, difficult combustion.
Comparative example 7:
Get 20% (w) styrene-butadiene latex 500g, add the commercially available separant potassium rosinate of 200g, add 0.5g commodity TDE, stir and make it to mix, add 100g Al
2(SO
4)
3condense, controlling condensing field temperature is 80 DEG C, and obtain slurry and obtain powdered rubber after washing drying, surveying its oxygen index is 20.8%, and flame retardant effect is not good.
Claims (5)
1. a preparation method for flame retardant type separant, is characterized in that comprising the following steps:
1) be (0.1 ~ 6) with unsaturated fatty acids acid anhydrides according to mol ratio by halogenic donator: the ratio of 1 mixes, stir, add initiator, the mol ratio of initiator and unsaturated fatty acids acid anhydrides is (0 ~ 3): 1, carries out the addition reaction of 0.5 ~ 5 hour at 30 ~ 150 DEG C of temperature;
2) to step 1) reaction solution in add excessive dilute alkaline aqueous solution, regulate the pH value of reaction solution to be greater than 8, stir and make product in 0.1 ~ 2 hour, obtain flame retardant type separant; Described halogenic donator is tetracol phenixin, hydrogenchloride, chlorine, hydrogen bromide, bromine; Described unsaturated fatty acids acid anhydrides is selected from acrylic anhydride, iso-butylene acid anhydrides, monoene caproic anhydride, monoene lauric anhydride, monoene stearic acid acid anhydride, diene stearic acid acid anhydride or triolefin stearic acid acid anhydride.
2. preparation method as claimed in claim 1, adopts the mode advertised that circulates to pass in reactive component when it is characterized in that described halogenic donator is gas.
3. preparation method as claimed in claim 1, is characterized in that described initiator is benzoyl peroxide, dicumyl peroxide, di-isopropylbenzene hydroperoxide or oxygen.
4. preparation method as claimed in claim 1, it is characterized in that described alkali aqueous solution is sodium hydroxide, potassium hydroxide or ammoniacal liquor, the mass concentration of alkali aqueous solution is 2% ~ 50%.
5. the application of flame retardant type separant in styrene-butadiene latex, nitrile rubber, natural rubber latex or polybutadiene latex agglomeration process adopting method as claimed in claim 1 to obtain, for the preparation of the powdered rubber with anti-flaming function.
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|---|---|---|---|
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| CN103159611B true CN103159611B (en) | 2014-12-24 |
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| CN104448446B (en) * | 2013-09-18 | 2016-08-17 | 中国石油天然气股份有限公司 | A kind of preparation method of environmental-protection flame-retardant powder styrene butadiene rubber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569906A (en) * | 2003-07-17 | 2005-01-26 | 中国石油天然气股份有限公司 | Continuous method for agglomeration preparation of powdered rubber |
| CN1704439A (en) * | 2004-06-02 | 2005-12-07 | 中国石油天然气股份有限公司 | Method for making powdered rubber |
| CN102070789A (en) * | 2009-11-25 | 2011-05-25 | 中国石油天然气股份有限公司 | Preparation method of powder rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5938206A (en) * | 1982-08-30 | 1984-03-02 | Toyo Soda Mfg Co Ltd | Prevention of coagulation of powdered rubber |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569906A (en) * | 2003-07-17 | 2005-01-26 | 中国石油天然气股份有限公司 | Continuous method for agglomeration preparation of powdered rubber |
| CN1704439A (en) * | 2004-06-02 | 2005-12-07 | 中国石油天然气股份有限公司 | Method for making powdered rubber |
| CN102070789A (en) * | 2009-11-25 | 2011-05-25 | 中国石油天然气股份有限公司 | Preparation method of powder rubber |
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| Title |
|---|
| JP昭59-38206A 1984.03.02 * |
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