CN103834055A - Low temperature environment-friendly foaming agent - Google Patents
Low temperature environment-friendly foaming agent Download PDFInfo
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- CN103834055A CN103834055A CN201410104864.8A CN201410104864A CN103834055A CN 103834055 A CN103834055 A CN 103834055A CN 201410104864 A CN201410104864 A CN 201410104864A CN 103834055 A CN103834055 A CN 103834055A
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- temperature environment
- whipping agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
Abstract
The invention provides a low temperature environment-friendly foaming agent. The foaming agent comprises 40-80 parts of AC foaming agent, 10-40 parts of active additive, 1-10 parts of decomposing control agent, and 5-20 parts of formamide removing agent, wherein the active additive is a single active additive A or a mixture of active additive A, active additive B and active additive C, the active additive A is zinc compounds like zinc oxide, zinc stearate and the like, the active additive B is urea or thiourea for surface treatment, the active additive C is one of triethanolamine, pentaerythritol and glycerinum or mixture of a plurality of triethanolamine, pentaerythritol and glycerinum. The low temperature environment-friendly foaming agent has low decomposing temperature; furthermore, the decomposed product is completely free of formaldehyde and basically contains no formamide.
Description
Technical field
The invention belongs to chemical foaming agent field, especially a kind of low-temperature environment-friendly whipping agent.
Background technology
AC whipping agent is that a kind of gas forming amount is large, superior performance, broad-spectrum whipping agent.The chemical name of AC whipping agent is Cellmic C 121, and it is widely used in various synthetic materialss, and its application spreads all over the industries such as slippers, sole, shoe-pad, plastic wallpaper, top ceiling, flooring laminate, leatheroid, thermal insulation, sound-proof material.And, due to AC whipping agent have stable performance, nonflammable, do not pollute, nonpoisonous and tasteless, on mould do not corrode on goods do not dye, decomposition temperature is adjustable, do not affect and solidify and the feature such as shaping speed, it has broad application prospects.
Although AC whipping agent is of many uses, but, there is following shortcoming in existing AC whipping agent (Cellmic C 121): (1) AC foaming agent decomposition temperature is at 200～208 DEG C, even if add the activator such as zinc oxide, zinc carbonate composition compound foaming agent in AC whipping agent, the decomposition temperature of compound foaming agent is also more than 155 DEG C, and decomposition temperature is high; (2) because the decomposition reaction of AC whipping agent is a violent thermopositive reaction, the decomposition reaction of adding the AC whipping agent being caused by zn cpds is too quick, make that decomposition caused heat release is too concentrated, decomposition course is uncontrollable, easily cause the generation of second order reaction, produce some poisonous, harmful products, for example, when AC whipping agent decomposes at the temperature higher than 160 DEG C, can produce toxic substance-methane amide, have a strong impact on the healthy of user.The western countries such as European Union propose high requirement (require in goods methane amide content lower than 10 ppm) to methane amide content in foaming product, and adopt methane amide output in the foaming product that common AC whipping agent makes to be generally 150～500ppm, also have a strong impact on and restricting the export trade of China.
At present, for above-mentioned shortcoming (1), the composite modified production of low-temperature foaming agent of a kind of AC has been developed in home and abroad, and main raw is AC whipping agent (Cellmic C 121), H whipping agent (dinitrosopentamethlyene tetramine), urea fat.Although the decomposition temperature of the composite modified production of low-temperature foaming agent of this AC is 125～135 DEG C,, because this product contains H whipping agent, H whipping agent can produce another kind of toxic substance-formaldehyde in the time decomposing, and therefore, H whipping agent is also listed in the row of forbidding chemical by American-European countries.For above-mentioned shortcoming (2), way being is all is being researched and solved in home and abroad, still, does not also have breakthrough.
Summary of the invention
The present invention aims to provide a kind of low-temperature environment-friendly whipping agent that can solve the problems of the technologies described above, and this whipping agent not only decomposition temperature is low, and meanwhile, degradation production does not contain formaldehyde completely, and, in degradation production, be also substantially devoid of methane amide.
A kind of low-temperature environment-friendly whipping agent, by 40 ~ 80 parts of AC whipping agents, 10 ~ 40 parts of coagents, decompose 1 ~ 10 part of control agent, 5 ~ 20 parts of compositions of methane amide remover, wherein, coagent is single coagent A or coagent A, B, C three's mixture, coagent A is to toluenesulfinic acid zinc, benzene sulfinic acid zinc, tosic acid zinc, ZINC P-PHENOLSULFONATE, zinc citrate, zinc lactate, a kind of or several combination in Zinic stearas, coagent B is for using direactive glyceride, stearic acid, any one in oleic acid or several surface-treated urea or the thiocarbamide of carrying out, coagent C is trolamine, tetramethylolmethane, a kind of or several combination in glycerine, decomposition control agent is a kind of or several combination in hexamethylenetetramine, sodium nitrilo triacetate, nitrilotriacetic acid, sodium ethylene diamine tetracetate, methane amide remover is a kind of or several combination in diethyl malonate, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide.
Useful technique effect of the present invention is:
(1) in prior art, conventionally reduce AC foaming agent decomposition temperature by adding the zinc compounds such as zinc oxide, Zinic stearas, its decomposition temperature is generally more than 155 DEG C, and the present invention is by the selection to coagent, make the decomposition temperature of AC whipping agent be reduced to 135 DEG C of left and right, and the degradation production of coagent is not completely containing formaldehyde;
(2) the present invention is decomposed control agent and is slowed down the decomposition rate of AC by interpolation, make decomposition reaction become mild, heat release is even, prevent the too high generation that causes a series of second order reactions of local temperature, thereby, the generation of poisonous and harmful substances (being methane amide) reduced, simultaneously, the decomposition control agent that the present invention adopts is that itself is nontoxic, harmless, and, also nontoxic chemical substance of its degradation production;
(3) be further to reduce the hazardous and noxious substances in degradation production, the goods of guaranteeing to fire are nontoxic, the present invention is by adding some methane amide removers, and, the present invention, by methane amide remover is selected, can react with methane amide methane amide remover, thereby reaches the object of eliminating methane amide, meanwhile, the reaction product of guarantee methane amide remover itself and methane amide remover and methane amide is all nontoxic, harmless to human body;
(4) inventor is through test many times, obtain the better parameters combination scheme of AC whipping agent, coagent, decomposition control agent, methane amide remover deal, make finally can obtain the low-temperature environment-friendly whipping agent of high gas forming amount, low decomposition temperature, zero formaldehyde and the discharge of low methane amide.
A method of preparing above-mentioned low-temperature environment-friendly whipping agent, comprises the following steps:
(1) get 40 ~ 80 parts of AC whipping agents, 10 ~ 40 parts of coagents, decompose 1 ~ 10 part of control agent, 5 ~ 20 parts of methane amide removers, mix;
(2) comminuting matter;
(3) employing 300～450 orders sieve to remove and do not pulverize coarse particles completely;
(4) fine particle after thick to grinding screen carries out secondary mixing, obtains low-temperature environment-friendly whipping agent product.
The preparation method of low-temperature environment-friendly whipping agent of the present invention has adopted secondary mixing, and the uniformity coefficient of prepared low-temperature environment-friendly whipping agent is higher, makes the function of each moiety of low-temperature environment-friendly whipping agent obtain maximum release; In addition, the present invention pulverizes material by step (2), and the grain diameter after pulverizing is limited, and makes the grain diameter of the prepared low-temperature environment-friendly whipping agent of the present invention less, improve the direct contact area of different components, further improved uniformity coefficient.
The mass ratio of coagent A, B, C is preferably: 1 ~ 1.5: 4: 1 ~ 1.5 o'clock, can reduce below decomposition temperature to 135 DEG C.
In addition, in order to save the cost of coagent of the present invention, make the decomposition temperature of obtained whipping agent minimum, coagent preferably adds 20 ~ 30 parts simultaneously.In order to save the cost of decomposition control agent of the present invention, the amount of methane amide is down to minimum, meanwhile, keep suitable rate of decomposition, decompose control agent and preferably add 3 ~ 5 parts.In order to save the cost of methane amide remover of the present invention, methane amide remover preferably adds 5 ~ 8 parts.
In specific implementation process, above-mentioned steps (3) preferably adopts micronizer mill to pulverize material, certainly, pulverising step herein also can adopt other grinding mode, for example: mechanical mill etc., still, adopt the pulverizing of micronizer mill fastest, and, in crushing process, be not easy to pollute other impurity.
In addition, the pulverising step in above-mentioned steps (2) is preferably crushing material is pulverized to its median size is 3～5 microns, like this, can greatly reduce returning charge rate.
Embodiment
A kind of low-temperature environment-friendly whipping agent, by 40 ~ 80 parts of AC whipping agents, 10 ~ 40 parts of coagents, decompose 1 ~ 10 part of control agent, 5 ~ 20 parts of compositions of methane amide remover, wherein, coagent is single coagent A or coagent A, B, C three's mixture, coagent A is to toluenesulfinic acid zinc, benzene sulfinic acid zinc, tosic acid zinc, ZINC P-PHENOLSULFONATE, zinc citrate, zinc lactate, a kind of or several combination in Zinic stearas, coagent B is for using direactive glyceride, stearic acid, any one in oleic acid or several surface-treated urea or the thiocarbamide of carrying out, coagent C is trolamine, tetramethylolmethane, a kind of or several combination in glycerine, decomposition control agent is a kind of or several combination in hexamethylenetetramine, sodium nitrilo triacetate, nitrilotriacetic acid, sodium ethylene diamine tetracetate, methane amide remover is a kind of or several combination in diethyl malonate, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide.
A method of preparing above-mentioned low-temperature environment-friendly whipping agent, comprises the following steps:
(1) get 40 ~ 80 parts of AC whipping agents, 10 ~ 40 parts of coagents, decompose 1 ~ 10 part of control agent, 5 ~ 20 parts of methane amide removers, close evenly;
(2) adopt micronizer mill comminuting matter, it is 3～5 microns that crushing material is pulverized to its median size;
(3) employing 300～450 orders sieve to remove and do not pulverize coarse particles completely;
(4) fine particle after thick to grinding screen carries out secondary mixing, obtains low-temperature environment-friendly whipping agent product.
Certainly, above-mentioned steps (2) also can adopt other grinding mode, for example: mechanical mill etc., still, adopt the pulverizing of micronizer mill fastest, and, in crushing process, be not easy to pollute other impurity.In addition, the pulverising step in above-mentioned steps (2) also can only be pulverized crushing material for being greater than 5 microns to its median size, and still, like this, after sieving, coarse particles content is large, and returning charge rate is high.
Because coagent, decomposition control agent and methane amide remover in the formula of low-temperature environment-friendly whipping agent of the present invention all exist a large amount of array modes, therefore, embodiments of the invention One's name is legion.The applicant has intercepted part embodiment (embodiment 1 ~ embodiment 22) index of the low-temperature environment-friendly whipping agent making has been measured.In addition, the meaning limiting in order to embody coagent of the present invention, decomposition control agent and methane amide remover parameter, the applicant also provides 8 comparative examples (contrast 23 ~ contrast 30).Now list embodiments of the invention 1 ~ 22 and contrast 23 ~ 30 one-tenth is grouped into and composition umber (table 1 ~ 2, wherein, table 1 has been listed the deal of AC whipping agent in each embodiment, moiety and the deal of coagent; Table 2 has been listed and in each embodiment, has been decomposed the moiety of control agent and moiety and the deal of deal and methane amide).
Table 1
Table 2
By measuring the foaming situation of low-temperature environment-friendly whipping agent of the present invention at each temperature section, determine the minimum blowing temperature of whipping agent, i.e. lowest decomposition temperature.Meanwhile, by the gas forming amount in the analytical unit time, calculate rate of decomposition.Wherein, the concrete measuring method of the gas forming amount of this patent whipping agent is that the gas forming amount testing method providing according to rower (HG/T 2097-2008) is measured.
Prepare low-temperature environment-friendly whipping agent according to the method for preparing low-temperature environment-friendly whipping agent of the present invention, then adopt this low-temperature environment-friendly whipping agent to carry out pvc material (being called for short " PVC ") injection molding application test.
PVC injection molding application test formula (unit: part)
PVC （ SG7 ） 95~110
DOP 50~65
Low-temperature environment-friendly whipping agent 1.5 ~ 2.2 of the present invention
Lead sulfate tribasic 1.7 ~ 2.4
Lead stearate 0.8 ~ 1.1
Titanium dioxide 2.0 ~ 3.0
Calcium carbonate 19 ~ 26
Stearic acid 1.0 ~ 1.5
PVC moulded from foam technique: weighed material by formula, banburying 15 minutes in input Banbury mixer, on opening rubber mixing machine, 80 DEG C of left and right are opened and are smelt sheet again, cut-parts take 90 grams of sizing materials, put into 140 DEG C of vulcanizing presses, foam 10 minutes, after depanning cooling one hour, measure the content of methane amide and formaldehyde.
Now list the test-results (in table 3) of embodiments of the invention 1 ~ 22 and contrast 23 ~ 30:
Table 3
From the embodiment 1 ~ 22 in table 3, low-temperature environment-friendly whipping agent of the present invention is in the situation that can being down to 128 ~ 140 DEG C by lowest decomposition temperature, also can delay rate of decomposition to 0.61 mL/ (gmin), thereby, reduce methane amide content to 9.5 ppm following (meeting methane amide content in the foaming product that European Union the formulates standard lower than 10ppm), meanwhile, keep high gas forming amount (159 ~ 179 mL/g) and do not produce formaldehyde.And in the time that coagent is 20 ~ 30 parts, the lowest decomposition temperature of low-temperature environment-friendly whipping agent is seen the minimum level that can maintain 129 ~ 133 DEG C; In the time that decomposition control agent is 3 ~ 5 parts, can be by the level of maintain≤4.5ppm of the amount of methane amide.
In addition, can find out from table 1,2,3 embodiment 7,8,11 and 12 and the contrast of other embodiment, when the mass ratio of coagent A, B, C is: 1 ~ 1.5: 4: 1 ~ 1.5 time; Also can reduce below decomposition temperature to 135 DEG C.
Can find out from table 1,2,3 contrast 26, contrast 27, in the time that the deal of AC whipping agent is higher, decomposition temperature still higher than 160 DEG C, methane amide content higher than 10ppm, cannot meet the requirement of market to quality product; In the time that the deal of AC whipping agent is on the low side, although decomposition temperature, methane amide content all meet the requirements,, gas forming amount 87 mL/g, gas forming amount cannot meet the requirement to product.
Can find out from table 1,2,3 contrast 24, contrast 29, when suppressing the deal of decomposition agent when too high, rate of decomposition is down to 0.17 mL/ (gmin), and rate of decomposition is too low, impact foaming efficiency; In the time that inhibition decomposition agent deal is too low, rate of decomposition is too fast, causes methane amide content higher than 10ppm.
Can find out from table 1,2,3 contrast 25, contrast 25 adopts zinc oxide of the prior art and Zinic stearas as coagent, result: decomposition temperature is higher (being 165 DEG C), methane amide content higher (for 240.2ppm) still.
Can find out from table 1,2,3 contrast 28,30, in the time that methane amide remover deal is too low, methane amide content is far away higher than 10ppm; In the time that methane amide remover deal is too high, it is a kind of waste of cost.
In specific implementation process, above-mentioned steps (3) preferably adopts micronizer mill to pulverize material, certainly, pulverising step herein also can adopt other grinding mode, for example: mechanical mill etc., still, adopt the pulverizing of micronizer mill fastest, and, in crushing process, be not easy to pollute other impurity.
In addition, the pulverising step in above-mentioned steps (2) is preferably crushing material is pulverized to its median size is 3～5 microns, like this, can greatly reduce returning charge rate.
In the present invention used to toluenesulfinic acid zinc, benzene sulfinic acid zinc, tosic acid zinc, ZINC P-PHENOLSULFONATE all purchased from the special fine chemistry industry of Suzhou City's bass group, and be technical pure; Zinc citrate, zinc lactate, Zinic stearas, purchased from Nantong Feiyu Fine Chemicals Co., Ltd., are analytical pure; Trolamine is purchased from the analytical pure of Run Ji chemical industry limited liability company of Xinji City; Tetramethylolmethane is purchased from the technical pure of Kai Linruiyang chemical inc, Jiangsu; Glycerine is purchased from the technical pure of Weifang stars at dawn Chemical Industry Science Co., Ltd; Urotropine is purchased from the technical pure of Guangzhou Gui Hua Chemical Industry Science Co., Ltd; Sodium nitrilo triacetate, nitrilotriacetic acid are all purchased from the technical pure of Shanghai Hui Jin Chemical Co., Ltd.; Sodium ethylene diamine tetracetate is purchased from the technical pure of Baoding Kai Yue Chemical Co., Ltd.; Diethyl malonate is purchased from the technical pure of the sincere company limited in Hebei; Magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide are all purchased from the technical pure of Yingkou XinYao Mei industry company limited.
Claims (8)
1. a low-temperature environment-friendly whipping agent, by 40 ~ 80 parts of AC whipping agents, 10 ~ 40 parts of coagents, decompose 1 ~ 10 part of control agent, 5 ~ 20 parts of compositions of methane amide remover, wherein, coagent is single coagent A or coagent A, B, C three's mixture, coagent A is to toluenesulfinic acid zinc, benzene sulfinic acid zinc, tosic acid zinc, ZINC P-PHENOLSULFONATE, zinc citrate, zinc lactate, a kind of or several combination in Zinic stearas, coagent B is for using direactive glyceride, stearic acid, any one in oleic acid or several surface-treated urea or the thiocarbamide of carrying out, coagent C is trolamine, tetramethylolmethane, a kind of or several combination in glycerine, decomposition control agent is a kind of or several combination in hexamethylenetetramine, sodium nitrilo triacetate, nitrilotriacetic acid, sodium ethylene diamine tetracetate, methane amide remover is a kind of or several combination in diethyl malonate, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide.
2. a kind of low-temperature environment-friendly whipping agent according to claim 1, is characterized in that: the mass ratio of coagent A, B, C is: 1 ~ 1.5: 4: 1 ~ 1.5.
3. a kind of low-temperature environment-friendly whipping agent according to claim 1, is characterized in that: coagent is 20 ~ 30 parts.
4. a kind of low-temperature environment-friendly whipping agent according to claim 1, is characterized in that: decomposing control agent is 3 ~ 5 parts.
5. according to a kind of low-temperature environment-friendly whipping agent according to claim 1, it is characterized in that: methane amide remover is 5 ~ 8 parts.
6. a method of preparing any low-temperature environment-friendly whipping agent described in claim 1 ~ 5, is characterized in that, comprises the following steps:
(1) according to the deal of AC whipping agent claimed in claim 1, coagent, decomposition control agent, methane amide remover, mix;
(2) comminuting matter;
(3) employing 300～450 orders sieve to remove and do not pulverize coarse particles completely;
(4) fine particle after thick to grinding screen carries out secondary mixing, obtains low-temperature environment-friendly whipping agent product.
7. a kind of method of preparing low-temperature environment-friendly whipping agent according to claim 6, is characterized in that: step (3) adopts micronizer mill to pulverize material.
8. a kind of method of preparing low-temperature environment-friendly whipping agent according to claim 6, is characterized in that: in the pulverising step in step (2), crushing material being pulverized to its median size is 3～5 microns.
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| CN201610390592.1A CN105885078B (en) | 2014-03-20 | 2014-03-20 | The environment-friendly foaming agent of the low formaldehyde of decomposition product and its technique, coagent |
| CN201410104864.8A CN103834055B (en) | 2014-03-20 | 2014-03-20 | A kind of low-temperature environment-friendly whipping agent |
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| CN201410104864.8A CN103834055B (en) | 2014-03-20 | 2014-03-20 | A kind of low-temperature environment-friendly whipping agent |
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| CN201410104864.8A Active CN103834055B (en) | 2014-03-20 | 2014-03-20 | A kind of low-temperature environment-friendly whipping agent |
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| CN105504329A (en) * | 2015-12-23 | 2016-04-20 | 江苏索普（集团）有限公司 | Compound foaming agent for polyethylene chemical crosslinking foam material and preparation method of compound foaming agent |
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Cited By (9)
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| CN105504329A (en) * | 2015-12-23 | 2016-04-20 | 江苏索普（集团）有限公司 | Compound foaming agent for polyethylene chemical crosslinking foam material and preparation method of compound foaming agent |
| CN105504329B (en) * | 2015-12-23 | 2018-11-02 | 江苏索普（集团）有限公司 | The compounding foaming agent and preparation method thereof of expanded material is chemically crosslinked for polyethylene |
| CN105648837A (en) * | 2016-01-04 | 2016-06-08 | 金戈炜业（江苏）壁纸有限公司 | High-foaming coating for printing wallpaper |
| CN105860203A (en) * | 2016-04-26 | 2016-08-17 | 三斯达（江苏）环保科技有限公司 | Environment-friendly safe PE (polyethylene) foamed ground mat and preparation method thereof |
| CN106009026A (en) * | 2016-05-18 | 2016-10-12 | 广州市隆海橡塑有限公司 | Foaming agent, preparation method and application |
| CN106009026B (en) * | 2016-05-18 | 2018-11-30 | 广州市隆海橡塑有限公司 | A kind of foaming agent, preparation method and application |
| CN109369949A (en) * | 2018-09-19 | 2019-02-22 | 肇庆凯艺装饰制品有限公司 | A kind of environment-friendly type PS plastic foaming agent |
| CN110734570A (en) * | 2019-09-29 | 2020-01-31 | 浙江杰上杰新材料有限公司 | PVC (polyvinyl chloride) formamide-free foaming agent |
| CN114316374A (en) * | 2021-07-28 | 2022-04-12 | 广东省贵来新材料科技有限公司 | Degradable environmental-friendly express bag and production equipment thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105885078A (en) | 2016-08-24 |
| CN105885078B (en) | 2018-11-09 |
| CN103834055B (en) | 2016-04-20 |
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