CN102558698A - High heat-resistant flame-retardant halogen-free thermoplastic resin and method for preparing same - Google Patents
High heat-resistant flame-retardant halogen-free thermoplastic resin and method for preparing same Download PDFInfo
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- CN102558698A CN102558698A CN2011104432886A CN201110443288A CN102558698A CN 102558698 A CN102558698 A CN 102558698A CN 2011104432886 A CN2011104432886 A CN 2011104432886A CN 201110443288 A CN201110443288 A CN 201110443288A CN 102558698 A CN102558698 A CN 102558698A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses a high heat-resistant flame-retardant halogen-free thermoplastic resin and a method for preparing the high heat-resistant flame-retardant halogen-free thermoplastic resin. The high heat-resistant flame-retardant halogen-free thermoplastic resin is prepared by adding a random copolymer and a phosphate compound into a twin-screw extruder with the average residence time of 1-15 minutes, and carrying out reactive extrusion at 180-300 DEG C, wherein the random copolymer contains maleic anhydride and an aromatic vinyl monomer, and the phosphate compound contains an active hydrogen unit. The high heat-resistant flame-retardant halogen-free thermoplastic resin has stable flame retardance and good heat resistance and is the intrinsic flame-retardant resin which is formed by grafting a flame retardant onto the side chain of a thermoplastic resin composition. The high heat-resistant flame-retardant halogen-free thermoplastic resin has higher efficiency than the additive flame retardant and the same processing cost as the additive flame retardant.
Description
Technical field
The present invention relates to a kind of high heat-stable halogen-free combustion-proof thermoplastic resin and preparation method thereof.
Background technology
For styrene resin, the flame retardant products of the overwhelming majority are composite with the oxide compound or the salt of bromide fire retardant and antimony, are aided with that anti-dripping agent and some processing aids prepare.It is stable that such product has flame retardant properties, and therefore the characteristics of excellent processability are adopted widely.Along with intensive environmental protection cry more and more, brominated flame retardant more and more obtains people's attention to the harm of organism.Though at present, people still do not have clear and definite result to the kind of harmful halide-containing and to the harm of environment.But it has been generally acknowledged that the part halide-containing possibly cause accumulation in the organism; The gas that the part halide-containing produces after burning maybe be carcinogenic; Part volatility organohalogen compound can damage the ozone layer or the like.At present, International Power association (IEC), Japan packing all have relevant bill/instruction definition with circuit association tissues such as (JPCA) to the Halogen material; Quite a few famous electronic apparatus manufacturers such as ASUS, LENOVO, DELL, APPLE etc. have the non-halogen plan of material.
The conventional method for preparing halogen-free flame-retardant resin is to realize through the not halogen-containing fire retardant that in resin matrix, adds nitrogen phosphine system.Though this method is used extensively, also is to have it conspicuous insufficient, for example fire retardant is separated out, flame retardant properties instability etc.It mainly is because mostly the conventional now halogen-free flame retardants that uses is that the consistency of some micromolecular compounds and resin matrix is relatively poor that fire retardant is separated out.Flame retardant properties is unstable, mainly is can't realize homodisperse fully because fire retardant is extruded in the processing blended process at twin screw.
Therefore; Thereby the contriver hopes through on the thermoplastic resin molecular structure, modifying the performance of improving thermoplastic resin; Exactly fire retardant is directly introduced in the molecule of thermoplastic resin specifically, thereby obtained a kind of heat-resisting, thermoplastic resin that flame retardant properties is better.
Summary of the invention
The object of the present invention is to provide a kind of high heat-resistant halogen-free flame-retardant thermoplastic resin, described high heat-resistant halogen-free flame-retardant thermoplastic resin stable reaches UL94 vertical combustion grade in the thickness of 1.5～3.0mm, have good thermotolerance simultaneously.
Another object of the present invention is to provide the preparation method of said high heat-resistant halogen-free flame-retardant thermoplastic resin.
Above-mentioned purpose of the present invention is achieved through adopting following technical scheme:
A kind of preparation method of high heat-resistant halogen-free flame-retardant thermoplastic resin; Comprise the steps: to contain the random copolymers of maleic anhydride, aromatic vinyl monomer and contain the unitary phosphonate ester compound of active hydrogen that to add mean residence time be in 1～15 minute the twin screw extruder; Under 180～300 ℃; Remove fugitive constituent through reacting to extrude, obtain the high heat-resistant halogen-free flame-retardant thermoplastic resin;
The active hydrogen unit of phosphonate ester compound with contain that the unitary mol ratio of maleic anhydride is 0.1～5: 1 in the random copolymers of maleic anhydride, aromatic vinyl monomer, the unitary content of maleic anhydride accounts for 8～40% of the random copolymers weight that comprises maleic anhydride, aromatic vinyl monomer; When maleic anhydride content was lower than 8wt%, the copolymer resins second-order transition temperature was lower, and thermotolerance is not enough, and maleic anhydride content is during greater than 40wt%, and monomer has the trend of intensive alternating copolymerization, and it is limited that molecular weight increases, and the mechanical property of copolymer resins is relatively poor.
Here said phosphonate ester compound comprises phosphonic acid ester, phosphinate, phosphinate compounds.Phosphonate ester compound effect in the present invention is a kind of fire retardant of response type.The described unitary phosphonate ester compound of active hydrogen that contains of the application; " containing the active hydrogen unit " is under certain condition; In heating or solution; Can react with anhydride group, generate the Wasserstoffatoms of the stable compound that covalent linkage connects or contain the group of such Wasserstoffatoms, this active hydrogen unit can be hydroxyl, carboxyl or the amido on the alkyl or aryl of phosphonic acid ester; Or the hydrogen that directly links to each other on the phosphinate with P; Or the hydroxyl on phosphiinic acid ester compound alkyl or the aryl, carboxyl or amido; Or the hydrogen that directly links to each other on the phosphinate with P; Or the hydroxyl on phosphinic acid ester compound alkyl or the aryl, carboxyl or amido.
More specifically, the said unitary phosphonate ester compound of active hydrogen that contains, its structure is suc as formula shown in (I):
In the formula (I), R
1For Wasserstoffatoms or by the substituted carbonatoms of several hydroxyls, carboxyl or amido 1～18 alkyl, naphthenic base, aryl, heterocyclic radical; R
2, R
3Independently be selected from carbonatoms and be 1～18 alkyl, naphthenic base, aryl, heterocyclic radical; Or by the substituted carbonatoms of several hydroxyls, carboxyl or amido 1～18 alkyl, naphthenic base, aryl, heterocyclic radical; Or R
2With R
3The formation carbonatoms is 1～18 ring; N1, n2, n3 are 0 or 1, and n1, n2, n3 are not 0 simultaneously.
As a kind of more preferably scheme, the said unitary phosphonate ester compound of active hydrogen more preferably 4-aminocarbonyl phenyl-diphenylphosphine acid esters, 4-amido benzyl-diphenylphosphine acid esters, 4-aminocarbonyl phenyl-dibenzyl phosphonic acid ester, 4-aminocarbonyl phenyl-benzyl-Phenylphosphine acid esters, two (4-aminocarbonyl phenyl)-Phenylphosphine acid esters, two (4-amido benzyl)-Phenylphosphine acid esters, two (4-aminocarbonyl phenyl)-benzylphosphonic acid ester, two (4-amido benzyl)-benzylphosphonic acid ester, 4-hydroxy phenyl-diphenylphosphine acid esters, 4-hydroxybenzyl-diphenylphosphine acid esters, 4-hydroxy phenyl-dibenzyl phosphonic acid ester, 4-hydroxy phenyl-benzyl-Phenylphosphine acid esters, two (4-hydroxy phenyl)-Phenylphosphine acid esters, two (4-hydroxybenzyl)-Phenylphosphine acid esters, two (4-hydroxy phenyl)-benzylphosphonic acid ester or two (4-the hydroxybenzyl)-benzylphosphonic acid ester of containing.
The described unitary phosphonate ester compound of active hydrogen that contains can be in the above-mentioned phosphonate ester compound any one, or several kinds mixture.
Principle of the present invention is (1 the situation of all getting with n1, n2, n3 is an example, and other value principle is identical) as follows:
Contain maleic anhydride unit and the active hydrogen unit process in the phosphonate ester compound in the random copolymers of maleic anhydride, aromatic vinyl monomer, fire retardant is grafted on the resin matrix.
When containing a reactive hydrogen (like hydroxyl) on the R base, production 1 compound when containing two each and every one reactive hydrogens (like amido), is two-step reaction, the first step production 1 compound, second step production 2 compounds.
The said random copolymers that contains maleic anhydride, aromatic vinyl monomer described in the present invention can be by maleic anhydride unit, the two random copolymers of forming of aromatic vinyl monomer; Perhaps added the random copolymers of vinyl cyanide and/or diene units, promptly by at least a random copolymers of forming in maleic anhydride unit, aromatic vinyl monomer and vinyl cyanide or the diolefine.The interpolation of vinyl cyanide or diolefine can not influence effect of the present invention.
As a kind of preferred version, said aromatic vinyl monomer is preferably vinylbenzene, alpha-methyl styrene or p-methylstyrene.
As a kind of most preferably scheme, said aromatic vinyl monomer most preferably is vinylbenzene.
As a kind of preferred version, the active hydrogen unit of said phosphonate ester compound with comprise that the unitary mol ratio of maleic anhydride is preferably 0.2～3 in the random copolymers of maleic anhydride, aromatic vinyl monomer: 1.When mol ratio less than 0.2 the time, the add-on of fire retardant is few, flame retardant properties is not enough, mol ratio is greater than 3 o'clock, fire retardant can not complete reaction, there is no need.
As a kind of preferred version, the said molecular weight that contains the random copolymers of maleic anhydride, aromatic vinyl monomer is 0.5～250,000.
As a kind of preferred version, described twin screw extruder is preferably the exhaust twin screw extruder.
As a kind of preferred version, the said preparation method who contains the random copolymers of maleic anhydride, aromatic vinyl monomer and contain the unitary phosphonate ester compound of active hydrogen is a reaction extrusion.This reaction extrusion, the halogen-free flame-retardant resin of tooling cost and addition type is suitable; The halogen-free flame-retardant resin for preparing is the fire-retardant halogen-free combustion-proof thermoplastic resin of a kind of intrinsic.
The method of extruding through reaction will have the fire retardant of active reactive group and receive on the resin matrix through the method for chemically bonded; Both can solve because the fire retardant that compatibility problem causes is separated out; Also can realize effective dispersion of fire retardant, solve the problem of conventional additive flame retardant system.In addition, the method for extruding through reaction is the fire-retardant material of intrinsic with the resin that fire retardant is grafted to back preparation on the resin matrix, and still, its tooling cost is suitable with the method for adding blend.
Method among the present invention is that fire retardant is grafted on the side chain of resin, has improved the steric hindrance of molecular resin main chain space motion, can effectively improve the second-order transition temperature and the thermotolerance of resin matrix.Compare conventional high heat-resistant halogen-free flame-retardant resin material, like PC/ABS, the resin matrix that the present invention adopts is the random copolymers of styrene resin, and performances such as its cracking of anti-the solvent are more excellent.Simultaneously, because fire retardant is to receive on the resin matrix through the method for chemically bonded, the adding that can reduce fire retardant is to the influence of resin mechanical property etc., and improves the service efficiency of fire retardant, reduces addition, improves the cost performance of flame retardant products.
Compared with prior art, the present invention has following beneficial effect:
High heat-resistant halogen-free flame-retardant thermoplastic resin according to the invention has stable flame retardant properties, good heat-resistant; Described halogen-free combustion-proof thermoplastic resin be a kind of in grafting on thermoplastic resin composition's side chain the intrinsic flame-retarded resin of fire retardant, compare with additive flame retardant, the service efficiency of its fire retardant is higher; The tooling cost of said high heat-resistant halogen-free flame-retardant thermoplastic resin is suitable with the addition type halogen-free flame-retardant resin.
Embodiment
Further explain the present invention below in conjunction with specific embodiment, but embodiment does not do any type of qualification to the present invention.
The maleic anhydride-styrene random copolymers is provided by Polyscope company, and maleic anhydride content is the 8-40% weight ratio, and weight average molecular weight range is 0.5-25 ten thousand.The performance of the maleic anhydride-styrene random copolymers that uses among the present invention is as shown in table 1:
The performance data of table 1 maleic anhydride-styrene random copolymers
The second-order transition temperature of sample (Tg) is recorded by the anti-DSC DSC200 F3 that speeds of Germany, and heat-up rate is 10 ℃/min.
The vertical combustion grade judges that the standard of following is UL94.
Embodiment 1
Accurately taking by weighing maleic anhydride content is the maleic anhydride-styrene random copolymers and the 4-aminocarbonyl phenyl-diphenyl phosphoester of 28% weight ratio; Make wherein in the SULPHOSUCCINIC ACID ESTER that the unitary mol ratio of maleic anhydride is 1.5: 1 in the amido and maleic anhydride-styrene random copolymers; With two kinds of material thorough mixing, directly add the exhaust twin screw extruder, under 200-220 ℃, extrude; Venting port vacuum tightness is 0.02MPa, and mean residence time is 5min.
Embodiment 2
Accurately taking by weighing maleic anhydride content is the maleic anhydride-styrene random copolymers and the 4-hydroxy phenyl-diphenyl phosphoester of 28% weight ratio; Make wherein in the SULPHOSUCCINIC ACID ESTER that the unitary mol ratio of maleic anhydride is 1.5: 1 in the hydroxyl and maleic anhydride-styrene random copolymers; With two kinds of material thorough mixing, directly add the exhaust twin screw extruder, under 200-220 ℃, extrude; Venting port vacuum tightness is 0.02MPa, and mean residence time is 15min.
Embodiment 3
Accurately taking by weighing maleic anhydride content is the maleic anhydride-styrene random copolymers and two (4-aminocarbonyl phenyl)-phenyl phosphate ester of 15% weight ratio; Make wherein in the SULPHOSUCCINIC ACID ESTER that the unitary mol ratio of maleic anhydride is 3: 1 in the amido and maleic anhydride-styrene random copolymers; With two kinds of material thorough mixing, directly add the exhaust twin screw extruder, under 200-220 ℃, extrude; Venting port vacuum tightness is 0.02MPa, and mean residence time is 5min.
Embodiment 4
Accurately taking by weighing maleic anhydride content is the maleic anhydride-styrene random copolymers and two (4-hydroxy phenyl)-phenyl phosphate ester of 23% weight ratio; Make wherein in the SULPHOSUCCINIC ACID ESTER that the unitary mol ratio of maleic anhydride is 0.5: 1 in the hydroxyl and maleic anhydride-styrene random copolymers; With two kinds of material thorough mixing, directly add the exhaust twin screw extruder, under 300 ℃, extrude; Venting port vacuum tightness is 0.02MPa, and mean residence time is 5min.
Embodiment 5
Accurately taking by weighing maleic anhydride content is the maleic anhydride-styrene random copolymers and the 4-aminocarbonyl phenyl-diphenyl phosphoester of 40% weight ratio; Make wherein in the SULPHOSUCCINIC ACID ESTER that the unitary mol ratio of maleic anhydride is 0.1: 1 in the amido and maleic anhydride-styrene random copolymers; With two kinds of material thorough mixing, directly add the exhaust twin screw extruder, under 250 ℃, extrude; Venting port vacuum tightness is 0.02MPa, and mean residence time is 1min.
Embodiment 6
Accurately taking by weighing maleic anhydride content is the maleic anhydride-styrene random copolymers and the 4-aminocarbonyl phenyl-diphenyl phosphoester of 8% weight ratio; Make wherein in the SULPHOSUCCINIC ACID ESTER that the unitary mol ratio of maleic anhydride is 5: 1 in the amido and maleic anhydride-styrene random copolymers; With two kinds of material thorough mixing, directly add the exhaust twin screw extruder, under 180 ℃, extrude; Venting port vacuum tightness is 0.02MPa, and mean residence time is 10min.
Comparative Examples 1
Accurately taking by weighing maleic anhydride content is the maleic anhydride-styrene random copolymers and the triphenylphosphate (TPP) of 28% weight ratio; Make wherein in the SULPHOSUCCINIC ACID ESTER that the unitary mol ratio of maleic anhydride is 0.5: 1 in the P element and maleic anhydride-styrene random copolymers; With two kinds of material thorough mixing, directly add the exhaust twin screw extruder, under 200-220 ℃, extrude; Venting port vacuum tightness is 0.02MPa, and mean residence time is 5min.
More than the second-order transition temperature and the vertical combustion test result of each embodiment and comparative example as shown in table 2:
The performance data of each embodiment of table 2 and comparative example
Claims (9)
1. the preparation method of a high heat-resistant halogen-free flame-retardant thermoplastic resin is characterized in that, comprises the steps:
To contain the random copolymers of maleic anhydride, aromatic vinyl monomer and contain the unitary phosphonate ester compound of active hydrogen that to add mean residence time be in 1～15 minute the twin screw extruder; Under 180～300 ℃; Extrude through reaction, obtain the high heat-resistant halogen-free flame-retardant thermoplastic resin;
The active hydrogen unit of phosphonate ester compound with contain that the unitary mol ratio of maleic anhydride is 0.1～5: 1 in the random copolymers of maleic anhydride, aromatic vinyl monomer, the unitary content of maleic anhydride accounts for 8～40% of the random copolymers weight that contains maleic anhydride, aromatic vinyl monomer.
2. the preparation method of high heat-resistant halogen-free flame-retardant thermoplastic resin according to claim 1; It is characterized in that the said random copolymers that contains maleic anhydride, aromatic vinyl monomer is by at least a composition the in maleic anhydride unit, aromatic vinyl monomer and vinyl cyanide or the diolefine.
3. the preparation method of high heat-resistant halogen-free flame-retardant thermoplastic resin described in claim 1 or 2 is characterized in that, said aromatic vinyl monomer is vinylbenzene, alpha-methyl styrene or p-methylstyrene.
4. like the preparation method of the said high heat-resistant halogen-free flame-retardant thermoplastic resin of claim 3, it is characterized in that said aromatic vinyl monomer is a vinylbenzene.
5. the preparation method of high heat-resistant halogen-free flame-retardant thermoplastic resin according to claim 1 is characterized in that, the said unitary phosphonate ester compound of active hydrogen that contains, and its structure is suc as formula shown in (I):
In the formula (I), R
1For Wasserstoffatoms or by the substituted carbonatoms of several hydroxyls, carboxyl or amido 1～18 alkyl, naphthenic base, aryl, heterocyclic radical; R
2, R
3Independently be selected from carbonatoms and be 1～18 alkyl, naphthenic base, aryl, heterocyclic radical; Or by the substituted carbonatoms of several hydroxyls, carboxyl or amido 1～18 alkyl, naphthenic base, aryl, heterocyclic radical; Or R
2With R
3The formation carbonatoms is 1～18 ring; N1, n2, n3 are 0 or 1, and n1, n2, n3 are not 0 simultaneously.
6. like the preparation method of the said high heat-resistant halogen-free flame-retardant thermoplastic resin of claim 5; It is characterized in that the said unitary phosphonate ester compound of active hydrogen that contains is 4-aminophenyl-diphenylphosphine acid esters, 4-aminobenzyl-diphenylphosphine acid esters, 4-aminophenyl-dibenzyl phosphonic acid ester, 4-aminophenyl-benzyl-Phenylphosphine acid esters, two (4-aminophenyl)-Phenylphosphine acid esters, two (4-aminobenzyl)-Phenylphosphine acid esters, two (4-aminophenyl)-benzylphosphonic acid ester, two (4-aminobenzyl)-benzylphosphonic acid ester, 4-hydroxy phenyl-diphenylphosphine acid esters, 4-hydroxybenzyl-diphenylphosphine acid esters, 4-hydroxy phenyl-dibenzyl phosphonic acid ester, 4-hydroxy phenyl-benzyl-Phenylphosphine acid esters, two (4-hydroxy phenyl)-Phenylphosphine acid esters, two (4-hydroxybenzyl)-Phenylphosphine acid esters, two (4-hydroxy phenyl)-benzylphosphonic acid ester or two (4-hydroxybenzyl)-benzylphosphonic acid ester.
7. the preparation method of high heat-resistant halogen-free flame-retardant thermoplastic resin according to claim 1; It is characterized in that, the active hydrogen unit of said phosphonate ester compound with contain that the unitary mol ratio of maleic anhydride is 0.2～3: 1 in the random copolymers of maleic anhydride, aromatic vinyl monomer.
8. the preparation method of high heat-resistant halogen-free flame-retardant thermoplastic resin according to claim 1 is characterized in that the said molecular weight that contains the random copolymers of maleic anhydride, aromatic vinyl monomer is 0.5～250,000.
9. high heat-resistant halogen-free flame-retardant thermoplastic resin that makes by the preparation method of the said high heat-resistant halogen-free flame-retardant thermoplastic resin of claim 1.
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Cited By (7)
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| CN104845008A (en) * | 2015-05-12 | 2015-08-19 | 安徽雄亚塑胶科技有限公司 | Medical inflaming-retarding elastomer and preparation method thereof |
| CN109575190A (en) * | 2018-10-22 | 2019-04-05 | 佳易容相容剂江苏有限公司 | A kind of phosphorous polyethylene maleic anhydride graft copolymer and preparation method thereof with cooperative flame retardant effect |
| CN109983038A (en) * | 2016-10-26 | 2019-07-05 | 康宁公司 | Fire retardant polyolefin type resin and preparation method and the fiber optic cables for using the fire retardant polyolefin type resin |
| CN111205811A (en) * | 2020-01-17 | 2020-05-29 | 杭州启耀新材料有限公司 | Formula of flame-retardant adhesive film, roof antiskid waterproof plastic synthetic liner and manufacturing method thereof |
| US10882952B2 (en) | 2017-01-03 | 2021-01-05 | International Business Machines Corporation | Side-chain-functionalized polyhydroxyalkanoate materials |
| US10899880B2 (en) | 2016-12-02 | 2021-01-26 | International Business Machines Corporation | Functionalized polyhydroxyalkanoate materials formed from an unsaturated polyhydroxyalkanoate material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104845008A (en) * | 2015-05-12 | 2015-08-19 | 安徽雄亚塑胶科技有限公司 | Medical inflaming-retarding elastomer and preparation method thereof |
| CN109983038A (en) * | 2016-10-26 | 2019-07-05 | 康宁公司 | Fire retardant polyolefin type resin and preparation method and the fiber optic cables for using the fire retardant polyolefin type resin |
| US10899880B2 (en) | 2016-12-02 | 2021-01-26 | International Business Machines Corporation | Functionalized polyhydroxyalkanoate materials formed from an unsaturated polyhydroxyalkanoate material |
| US10882952B2 (en) | 2017-01-03 | 2021-01-05 | International Business Machines Corporation | Side-chain-functionalized polyhydroxyalkanoate materials |
| CN109575190A (en) * | 2018-10-22 | 2019-04-05 | 佳易容相容剂江苏有限公司 | A kind of phosphorous polyethylene maleic anhydride graft copolymer and preparation method thereof with cooperative flame retardant effect |
| CN111205811A (en) * | 2020-01-17 | 2020-05-29 | 杭州启耀新材料有限公司 | Formula of flame-retardant adhesive film, roof antiskid waterproof plastic synthetic liner and manufacturing method thereof |
| WO2024038847A1 (en) * | 2022-08-16 | 2024-02-22 | 株式会社レゾナック | Modified styrene-based elastomer |
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Address after: 300300 the Binhai New Area of Tianjin Airport Logistics Processing Zone Three West Road No. 166 A2-179 Patentee after: Tianjin Kingfa New Materials Co., Ltd. Patentee after: Kingfa Technology Co., Ltd. Patentee after: Shanghai Kingfa Science and Technology Development Co., Ltd. Patentee after: SICHUAN KINGFA TECHNOLOGY DEVELOPMENT CO., LTD. Address before: 300300 the Binhai New Area of Tianjin Airport Logistics Processing Zone Three West Road No. 166 A2-179 Patentee before: Tianjin Kingfa New Materials Co., Ltd. Patentee before: Kingfa Technology Co., Ltd. Patentee before: Shanghai Kingfa Science and Technology Development Co., Ltd. Patentee before: Mianyang Changxin New Material Development Co., Ltd. |