CN105885078B - The environment-friendly foaming agent of the low formaldehyde of decomposition product and its technique, coagent - Google Patents
The environment-friendly foaming agent of the low formaldehyde of decomposition product and its technique, coagent Download PDFInfo
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- CN105885078B CN105885078B CN201610390592.1A CN201610390592A CN105885078B CN 105885078 B CN105885078 B CN 105885078B CN 201610390592 A CN201610390592 A CN 201610390592A CN 105885078 B CN105885078 B CN 105885078B
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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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The present invention provides a kind of environment-friendly foaming agent of the low formaldehyde of decomposition product, 6~20 parts of 40~80 parts of AC foaming agents, 13~40 parts of coagent, 1~10 part of controlling agent of decomposition and formamide remover is taken to mix, wherein, coagent is the mixture of coagent A, B and C three, coagent A is the zinc class compounds such as zinc oxide, zinc stearate, coagent B is the urea or thiocarbamide of surface treatment, and coagent C is triethanolamine, pentaerythrite, one kind in glycerine or several combination.The present invention also provides a kind of techniques of the environment-friendly foaming agent of the low formaldehyde of coagent, decomposition product of the environment-friendly foaming agent of the low formaldehyde of decomposition product.The environment-friendly foaming agent of the low formaldehyde of decomposition product obtained by the present invention is at low cost, can keep high gas forming amount, product solidification and shaping speed are not influenced, and decomposition temperature is low, and decomposition product has been entirely free of formaldehyde, also it can meet requirement of the market to quality of item essentially free of formamide in decomposition product.
Description
Technical field
The present invention is application No. is 201410104864.8, and the applying date is on March 20th, 2014, a kind of entitled " low temperature
The divisional application of the application for a patent for invention of environment-friendly foaming agent ".The invention belongs to chemical foaming agent field, especially a kind of low temperature ring
Protect foaming agent.
Background technology
AC foaming agents are that a kind of gas forming amount is big, superior performance, widely used foaming agent.The chemical name of AC foaming agents is
Azodicarbonamide, it is widely used in various synthetic materials, and application spreads all over slippers, sole, insole, plastic wallpaper, smallpox
The industries such as plate, flooring laminate, artificial leather, thermal insulation, acoustic material.Also, since AC foaming agents have performance stable, nonflammable, no
Pollution, it is non-toxic and tasteless, mold is not corroded product is not dyed, decomposition temperature is adjustable, does not influence solidification and shaping speed etc.
Feature has broad application prospects.
Although AC foaming agents are widely used, existing AC foaming agents (azodicarbonamide) have the disadvantage that：
(1) AC foaming agent decomposition temperatures are at 200~208 DEG C, even if adding the activators such as zinc oxide, zinc carbonate composition in AC foaming agents
Compound foaming agent, for the decomposition temperature of compound foaming agent also at 155 DEG C or more, decomposition temperature is high；(2) due to AC foaming agents
Decomposition reaction is a violent exothermic reaction, along with the decomposition reaction of the AC foaming agents caused by zinc compound is excessively quick,
So that decomposition caused heat release is excessively concentrated, decomposes that course is uncontrollable, it is easy to cause the generation of second order reaction, it is toxic, harmful to generate some
Product, such as when AC foaming agents decompose at a temperature of higher than 160 DEG C, will produce noxious material-formamide, seriously affect use
The health of person.The western countries such as European Union propose high requirement (it is required that first in product the formamide content in foaming product
Amide content is less than 10ppm), and use made from common AC foaming agents in foaming product formamide yield be generally 150~
500ppm also seriously affects and restricts the export trade in China.
Currently, being directed to above-mentioned disadvantage (1), home and abroad has been developed for a kind of composite modified production of low-temperature foaming agent of AC, main
It is AC foaming agents (azodicarbonamide), H foaming agents (dinitrosopentamethlyene tetramine), urea fat to want material.Although this AC
The decomposition temperature of composite modified production of low-temperature foaming agent is 125~135 DEG C, and still, since the product contains H foaming agents, H foaming agents exist
It will produce another noxious material-formaldehyde when decomposition, therefore, H foaming agents are also included in the row of disabling chemicals by American-European countries.It is right
In above-mentioned disadvantage (2), home and abroad is all researching and solving method, still, is not there is breakthrough also.
Invention content
The present invention is intended to provide a kind of environment-friendly foaming agent of the low formaldehyde of the decomposition product that can solve above-mentioned technical problem, this
The low low-temperature environment-friendly foaming agent of decomposition temperature, decomposition product have been entirely free of formaldehyde, also, in decomposition product also substantially not
Contain formamide.
A kind of environment-friendly foaming agent of the low formaldehyde of decomposition product, takes 40~80 parts of AC foaming agents, coagent 13~40 part, point
6~20 parts of 1~10 part of solution controlling agent and formamide remover mix, wherein coagent is coagent A, B and C tri-
The mixture of person, coagent A are to toluenesulfinic acid zinc, benzenesulfinic acid zinc, p-methyl benzenesulfonic acid zinc, ZINC P-PHENOLSULFONATE, citric acid
One kind in zinc, zinc lactate and zinc stearate or several combination, coagent B are with monoglyceride, stearic acid and oleic acid
In any one or the several urea or thiocarbamide being surface-treated, coagent C is triethanolamine, pentaerythrite and sweet
One kind in oil or several combination；Decomposition controlling agent is hexamethylenetetramine, sodium nitrilo triacetate, nitrilotriacetic acid and second
One kind in sodium ethylene diamine tetracetate or several combination；Formamide remover is diethyl malonate, magnesia, hydroxide
One kind in magnesium, calcium oxide and calcium hydroxide or several combination.
The mass ratio of coagent A, B, C is：1~1.5:4:1~1.5.
It is 3~5 microns that the AC foaming agents, coagent, decomposition controlling agent and formamide remover, which are average grain diameter,
Fine grained.
A kind of coagent of the environment-friendly foaming agent of the low formaldehyde of decomposition product, the coagent are coagent A, B and C
The mixture of three, coagent A are to toluenesulfinic acid zinc, benzenesulfinic acid zinc, p-methyl benzenesulfonic acid zinc, ZINC P-PHENOLSULFONATE, lemon
One kind in sour zinc, zinc lactate and zinc stearate or several combination, coagent B are with monoglyceride, stearic acid and oil
Any one in acid or the several urea or thiocarbamide being surface-treated, coagent C be triethanolamine, pentaerythrite and
One kind in glycerine or several combination.
The mass ratio of described coagent A, B, C is：1~1.5:4:1~1.5.
The present invention advantageous effects be：
(1) usually the decomposition of AC foaming agents is reduced by adding the zinc class compounds such as zinc oxide, zinc stearate in the prior art
Temperature, decomposition temperature is generally at 155 DEG C or more, and the present invention passes through the selection to coagent so that point of AC foaming agents
Solution temperature is reduced to 135 DEG C or so, also, the decomposition product of coagent is entirely free of formaldehyde；
(2) present invention decomposes controlling agent to slow down the decomposition rate of AC by addition, so that decomposition reaction is become flat, heat release
Uniformly, a series of excessively high generation for leading to second order reactions of local temperature is prevented, to reduce poisonous and harmful substances (i.e. formyl
Amine) generation, meanwhile, the decomposition controlling agent that the present invention uses is nontoxic for itself, harmless, also, its decomposition product is also nontoxic
Harmless chemical substance；
(3) it is the poisonous and harmful substance being further reduced in decomposition product, it is ensured that product of firing is nontoxic, and the present invention is logical
It crosses and adds some formamide removers, also, the present invention is by selecting formamide remover so that formamide remover
It can react with formamide, to achieve the purpose that eliminate formamide, meanwhile, ensure formamide remover itself and first
The reaction product of amide remover and formamide is nontoxic, harmless to human body；
(4) the present inventor obtains AC foaming agents, coagent, decomposes controlling agent, formamide removal by testing many times
The preferable parameter combination scheme of agent deal so that finally can get high gas forming amount, low decomposition temperature, zero formaldehyde and low formyl
The low-temperature environment-friendly foaming agent of amine emission.
A kind of technique of the environment-friendly foaming agent of the low formaldehyde of decomposition product, includes the following steps：
(1) AC foaming agents described in accordance with the claim 1, coagent, the part for decomposing controlling agent, formamide remover
Amount, is mixed；
(2) comminuting matter；
(3) 300~450 mesh are used to be sieved；
(4) fine grained to grinding screen after thick carries out secondary mixing, obtains environment-friendly foaming agent product.
A kind of technique of the environment-friendly foaming agent of the low formaldehyde of decomposition product, AC foaming agents as described above, coagent,
The deal for decomposing controlling agent, formamide remover, obtains environment-friendly foaming agent product after mixing.
The technique of the environment-friendly foaming agent of the low formaldehyde of decomposition product of the present invention uses secondary mixing, obtained low temperature ring
Protect the uniformity higher of foaming agent so that the function of each constituent of low-temperature environment-friendly foaming agent obtains maximum release；Separately
Outside, the present invention crushes material by step (2), is defined to the grain diameter after crushing so that the present invention
The grain diameter smaller of obtained low-temperature environment-friendly foaming agent improves the direct contact area of different component, further increases
The uniformity.
The mass ratio of coagent A, B, C is preferably：1~1.5:4:When 1~1.5, can reduce decomposition temperature to 135 DEG C with
Under.
In addition, the cost of the coagent in order to save the present invention, while making the decomposition temperature of obtained foaming agent
Minimum, coagent is preferably added to 20~30 parts.In order to save the cost for decomposing controlling agent of the present invention, the amount of formamide is dropped
It is extremely minimum, meanwhile, decomposition rate appropriate is kept, controlling agent is decomposed and is preferably added to 3~5 parts.In order to save the formyl of the present invention
The cost of amine remover, formamide remover are preferably added to 5~8 parts.
In specific implementation process, above-mentioned steps (3) preferably crush material using airslide disintegrating mill, certainly, this
Other grinding modes can also be used in the pulverising step at place, such as：Mechanical lapping etc., still, using the crushing of airslide disintegrating mill
It is fastest, also, other impurities easy to pollute are not allowed in crushing process.
In addition, it is 3~5 micro- that the pulverising step in above-mentioned steps (2), which preferably crushes crushing material to its average grain diameter,
Rice, in this way, returning charge rate can be substantially reduced.
Specific implementation mode
A kind of environment-friendly foaming agent of the low formaldehyde of decomposition product, the low low-temperature environment-friendly foaming agent of this decomposition temperature decompose
Product is zero formaldehyde, by 40~80 parts of AC foaming agents, 10~40 parts of coagent, decomposes 1~10 part of controlling agent, formamide removal
5~20 parts of compositions of agent, wherein coagent is the mixture of single coagent A or coagent A, B, C three, activity
Auxiliary agent A is to toluenesulfinic acid zinc, benzenesulfinic acid zinc, p-methyl benzenesulfonic acid zinc, ZINC P-PHENOLSULFONATE, zinc citrate, zinc lactate, stearic acid
One kind in zinc or several combination, coagent B be in monoglyceride, stearic acid, oleic acid any one or it is several
The urea or thiocarbamide that kind is surface-treated, coagent C are triethanolamine, pentaerythrite, one kind in glycerine or several
Combination；Decomposition controlling agent is one in hexamethylenetetramine, sodium nitrilo triacetate, nitrilotriacetic acid, sodium ethylene diamine tetracetate
Kind or several combination；Formamide remover is in diethyl malonate, magnesia, magnesium hydroxide, calcium oxide, calcium hydroxide
One kind or several combination.
A method of above-mentioned low-temperature environment-friendly foaming agent is prepared, is included the following steps：
(1) 40~80 parts of AC foaming agents are taken, 10~40 parts of coagent, decompose 1~10 part of controlling agent, formamide remover
It 5~20 parts, closes uniform；
(2) airslide disintegrating mill comminuting matter is used, it is 3~5 microns that crushing material to its average grain diameter, which is crushed,；
(3) the sieving removal of 300~450 mesh is used not crush coarse granule completely；
(4) fine grained to grinding screen after thick carries out secondary mixing, obtains low-temperature environment-friendly foaming agent product.
Certainly, other grinding modes can also be used in above-mentioned steps (2), such as：Mechanical lapping etc., still, using air-flow
The crushing of pulverizer is fastest, also, other impurities easy to pollute are not allowed in crushing process.In addition, the powder in above-mentioned steps (2)
Quick short steps also can only crush crushing material to its average grain diameter for more than 5 microns suddenly, still, in this case, after sieving, coarse granule
Content is big, and returning charge rate is high.
Since coagent, decomposition controlling agent and formamide remover are equal in the formula of the low-temperature environment-friendly foaming agent of the present invention
There are a large amount of combinations, and therefore, the embodiment of the present invention is large number of.The applicant has intercepted section Example and (has implemented
1~embodiment of example 22) index of low-temperature environment-friendly foaming agent obtained is measured.In addition, in order to embody the activity of the present invention
Auxiliary agent decomposes the meaning that controlling agent and formamide removal agent parameter limit, and it is (right that the applicant additionally provides 8 comparative examples
30) than 23~comparison.Now list the embodiment of the present invention 1~22 and comparison 23~30 at being grouped as and ingredient number
(table 1~2, wherein table 1 lists the deal of AC foaming agents in each embodiment, the constituent of coagent and deal；
Table 2, which lists, decomposes the constituent of controlling agent and the constituent and deal of deal and formamide in each embodiment).
Table 1
Table 2
Low-temperature environment-friendly foaming agent by measuring the present invention determines the minimum of foaming agent in the foaming situation of each temperature section
Blowing temperature, i.e. lowest decomposition temperature.Meanwhile by the gas forming amount in the analytical unit time, calculating decomposition rate.Wherein, originally
The specific assay method of the gas forming amount of patent foaming agent is the gas forming amount test side provided according to rower (HG/T 2097-2008)
What method was measured.
Low-temperature environment-friendly foaming agent is prepared according to the method for the present invention for preparing low-temperature environment-friendly foaming agent, then uses
This low-temperature environment-friendly foaming agent carries out pvc material (referred to as " PVC ") injection moulding application test.
PVC moulded from foam techniques：Material has been weighed by formula, has put into mixing 15 minutes in mixer, then open refining glue
80 DEG C or so mills are in blocks on machine, and cut-parts weigh 90 grams of sizing materials, are put into vulcanizing press 140 DEG C, foam 10 minutes, after depanning
A cooling hour, measure the content of formamide and formaldehyde.
Now list the test result (being shown in Table 3) of the embodiment of the present invention 1~22 and comparison 23~30：
Table 3
By the Examples 1 to 22 in table 3 it is found that lowest decomposition temperature can be down to by the low-temperature environment-friendly foaming agent of the present invention
In the case of 128~140 DEG C, it can also delay decomposition rate to 0.61mL/ (gmin), to reduce formamide content extremely
9.5ppm or less (meets the standard that the formamide content in the foaming product of European Union's formulation is less than 10ppm), meanwhile, it keeps occurred frequently
Tolerance (159~179mL/g) and do not generate formaldehyde.Also, when coagent is 20~30 parts, low-temperature environment-friendly foaming agent is most
Low decomposition temperature, which is seen, can maintain 129~133 DEG C of floor level；It, can be by formamide when it is 3~5 parts to decompose controlling agent
Amount maintains the≤level of 4.5ppm.
In addition, can be seen that from the embodiment 7,8,11 and 12 of table 1,2,3 and the comparison of other embodiment, when coagent A,
B, the mass ratio of C is：1~1.5:4:When 1~1.5；Also decomposition temperature can be reduced to 135 DEG C or less.
It can be seen that, when the deal of AC foaming agents is higher, decomposition temperature is still high from comparison 26, the comparison 27 of table 1,2,3
It is higher than 10ppm in 160 DEG C, formamide content, cannot be satisfied requirement of the market to product quality；When the deal of AC foaming agents is relatively low
When, although decomposition temperature, formamide content meet the requirements, gas forming amount 87mL/g, gas forming amount cannot be satisfied to product
It is required that.
It can be seen that, when inhibiting the deal of distintegrant excessively high, decomposition rate is down to from comparison 24, the comparison 29 of table 1,2,3
0.17mL/ (gmin), decomposition rate is too low, influences bubbling efficiency；When inhibiting distintegrant deal too low, decomposition rate mistake
Soon, formamide content is caused to be higher than 10ppm.
It can be seen that from the comparison 25 of table 1,2,3, comparison 25 is using zinc oxide in the prior art and zinc stearate as work
Property auxiliary agent, as a result：Decomposition temperature still higher (for 165 DEG C), formamide content are higher (for 240.2ppm).
It can be seen that from the comparison 28,30 of table 1,2,3, when formamide remover deal is too low, formamide content is much high
In 10ppm；It is a kind of waste of cost when formamide remover deal is excessively high.
In specific implementation process, above-mentioned steps (3) preferably crush material using airslide disintegrating mill, certainly, this
Other grinding modes can also be used in the pulverising step at place, such as：Mechanical lapping etc., still, using the crushing of airslide disintegrating mill
It is fastest, also, other impurities easy to pollute are not allowed in crushing process.
In addition, it is 3~5 micro- that the pulverising step in above-mentioned steps (2), which preferably crushes crushing material to its average grain diameter,
Rice, in this way, returning charge rate can be substantially reduced.
It is used in the present invention that toluenesulfinic acid zinc, benzenesulfinic acid zinc, p-methyl benzenesulfonic acid zinc, ZINC P-PHENOLSULFONATE are purchased from
In bass spy's fine chemistry industry group of Suzhou City, and it is technical pure；Zinc citrate, zinc lactate, zinc stearate fly purchased from Nantong City
Space fine chemicals Co., Ltd is that analysis is pure；Triethanolamine is purchased from the analysis of Run Ji chemical industry Co., Ltd of Xinji City
It is pure；Pentaerythrite is purchased from the technical pure of the Jiangsu chemical inc Kai Linruiyang；Glycerine is purchased from Weifang stars at dawn chemical science and technology
The technical pure of Co., Ltd；Methenamine is purchased from the technical pure of Guangzhou Gui Hua Chemical Industry Science Co., Ltd；Sodium nitrilo triacetate,
Nitrilotriacetic acid is purchased from the technical pure of Shanghai Hui Jin Chemical Co., Ltd.s；Sodium ethylene diamine tetracetate has purchased from the triumphant more chemical industry in Baoding
The technical pure of limit company；Diethyl malonate is purchased from the technical pure of Hebei sincerity Co., Ltd；Magnesia, magnesium hydroxide, oxidation
Calcium, calcium hydroxide are purchased from the technical pure of Yingkou XinYao Mei industry Co., Ltd.
Claims (5)
1. a kind of environment-friendly foaming agent of the low formaldehyde of decomposition product takes 40~80 parts of AC foaming agents, 13~40 parts of coagent, decomposes
6~20 parts of 1~10 part of controlling agent and formamide remover mix, wherein coagent is coagent A, B and C three
Mixture, coagent A be to toluenesulfinic acid zinc, benzenesulfinic acid zinc, p-methyl benzenesulfonic acid zinc, ZINC P-PHENOLSULFONATE, zinc citrate,
One kind in zinc lactate and zinc stearate or several combination, coagent B are in monoglyceride, stearic acid and oleic acid
Any one or the several urea or thiocarbamide being surface-treated, coagent C are in triethanolamine, pentaerythrite and glycerine
One kind or several combination；Decomposition controlling agent is hexamethylenetetramine, sodium nitrilo triacetate, nitrilotriacetic acid and ethylenediamine
One kind in tetraacethyl sodium or several combination；Formamide remover is diethyl malonate, magnesia, magnesium hydroxide, oxygen
Change calcium and one kind in calcium hydroxide or several combination.
2. the environment-friendly foaming agent of the low formaldehyde of decomposition product according to claim 1, it is characterised in that：Coagent A, B, C
Mass ratio be：1~1.5:4:1~1.5.
3. the environment-friendly foaming agent of the low formaldehyde of decomposition product according to claim 1, it is characterised in that：The AC foaming agents,
Coagent, decomposition controlling agent and formamide remover are the fine grained that average grain diameter is 3~5 microns.
4. a kind of technique of the environment-friendly foaming agent of the low formaldehyde of decomposition product, which is characterized in that include the following steps：
(1) AC foaming agents described in accordance with the claim 1, coagent, the deal for decomposing controlling agent, formamide remover, into
Row mixing；
(2) comminuting matter；
(3) 300~450 mesh are used to be sieved；
(4) fine grained to grinding screen after thick carries out secondary mixing, obtains environment-friendly foaming agent product.
5. a kind of technique of the environment-friendly foaming agent of the low formaldehyde of decomposition product, which is characterized in that AC hairs described in accordance with the claim 1
Infusion, coagent, the deal for decomposing controlling agent, formamide remover, obtain environment-friendly foaming agent product after mixing.
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| Application Number | Priority Date | Filing Date | Title |
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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 |
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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 Active CN103834055B (en) | 2014-03-20 | 2014-03-20 | A kind of low-temperature environment-friendly whipping agent |
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| 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 |
| 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 |
| CN110835435B (en) * | 2018-08-16 | 2023-01-13 | 东莞海丽化学材料有限公司 | Formamide absorbent, foaming agent composition and foaming material |
| 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 |
| CN113527768A (en) * | 2021-07-28 | 2021-10-22 | 东莞市智尊新材料科技有限公司 | Degradable environmental-friendly express bag and production equipment thereof |
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| CN1408748A (en) * | 2002-09-09 | 2003-04-09 | 宜兴市永鑫化工厂 | Plastic foaming and and its preparing method |
| CN101824189A (en) * | 2010-04-21 | 2010-09-08 | 北京市射线应用研究中心 | Preparation process of ethylene propylene diene rubber foaming materials |
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| CN105885078A (en) | 2016-08-24 |
| CN103834055A (en) | 2014-06-04 |
| CN103834055B (en) | 2016-04-20 |
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