CN115677968A - Formula and preparation method of non-yellowing polyurethane sponge - Google Patents
Formula and preparation method of non-yellowing polyurethane sponge Download PDFInfo
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- CN115677968A CN115677968A CN202211339625.1A CN202211339625A CN115677968A CN 115677968 A CN115677968 A CN 115677968A CN 202211339625 A CN202211339625 A CN 202211339625A CN 115677968 A CN115677968 A CN 115677968A
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Abstract
The invention discloses a formula of a non-yellowing polyurethane sponge and a preparation method thereof, wherein the formula of the non-yellowing polyurethane sponge comprises 95-110 parts of PPG, 0.5-1.5 parts of catalyst A, 0.5-1.0 part of catalyst B, 0.5-1.5 parts of silica gel, 1.0-3.0 parts of a cross-linking agent, 30-50 parts of TDI, 3-5 parts of water, 0.1-1.0 part of pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 0.1-1.0 part of bis (sebacate) (2, 6-tetramethyl-4-piperidyl), 0.1-1.0 part of 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazole-2-yl) phenol and tetraphenyl dipropylene glycol diphosphite. The invention introduces the anti-yellowing auxiliary agent containing pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, bis-sebacate (2, 6-tetramethyl-4-piperidyl), 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazole-2-yl) phenol and tetraphenyl dipropylene glycol diphosphite, so as to prepare the polyurethane which is not easy to turn yellow and inhibit scorching in the foaming process.
Description
Technical Field
The invention relates to a polyurethane sponge, in particular to a formula of a non-yellowing polyurethane sponge and a preparation method thereof.
Background
The polyurethane sponge is one kind of polyurethane foam plastic, belongs to soft polyurethane foam plastic, and is widely applied to the fields of clothing, packaging, automobiles, aviation, furniture and the like due to the advantages of low density, good elasticity, good air permeability, good water resistance, easily available raw materials and the like. At present, most sponge manufacturers still use aromatic isocyanates such as Toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) as raw materials, and because isocyanate groups in TDI and MDI are directly connected with benzene rings, yellowing is easily caused after long-term exposure to illumination and nitrogen oxide environments. During the production of the sponge, the production of polyurethane slabstock foams involves a violent exothermic reaction, and prolonged post-reaction thermal exposure can result in chemical changes that manifest as a blackening of the interior of the foam slabstock produced and are defined as scorch. In the production process of the sponge, the problem to be solved is how to inhibit scorching and make the produced sponge have good anti-yellowing performance.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a formula of a non-yellowing polyurethane sponge and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the formula of the non-yellowing polyurethane sponge comprises the following raw materials in parts by weight:
further, the anti-yellowing auxiliary agent comprises pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, bissebacate (2, 6-tetramethyl-4-piperidyl), 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazole-2-yl) phenol and tetraphenylpropylene glycol diphosphite, and the amount of the tetraphenylpropylene glycol diphosphite is 0.1-1% of the weight of the polyether glycol PPG.
Further, 95-100 parts of polyether glycol PPG, 0.5-1.0 part of catalyst A, 0.5-0.8 part of catalyst B, 0.5-1.0 part of silica gel, 1.5-2.5 parts of cross-linking agent and 35-45 parts of TDI 80.
Further, the polyether polyol PPG is 100 parts, the catalyst A is 1.0 part, the catalyst B is 0.8 part, the silica gel is 1.0 part, the crosslinking agent is 2.0 parts, and the TDI 80 is 40 parts.
Further, the polyether polyol PPG is polyether polyol PPG3000.
Further, the raw materials further include: 3-5 parts of water.
Furthermore, the catalyst A is triethylene diamine, the catalyst B is bis (dimethylaminoethyl) ether, and the crosslinking agent is trimethylolpropane.
A preparation method of the sponge comprises the following steps:
s1, weighing raw materials according to the weight parts of 95-110 parts of PPG, 0.5-1.5 parts of A, 0.5-1.0 part of B, 0.5-1.5 parts of silica gel, 1.0-3.0 parts of a cross-linking agent, 30-50 parts of TDI, 3-5 parts of water, 0.1-1.0 part of pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 0.1-1.0 part of bis (sebacate) (2, 6-tetramethyl-4-piperidyl), 0.1-1.0 part of 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazole-2-yl) phenol and 0.1-1.0 part of tetraphenyl dipropylene glycol diphosphite;
s2, mixing pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, bissebacate (2, 6-tetramethyl-4-piperidyl), 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazole-2-yl) phenol and tetraphenylpropylene glycol diphosphite into polyether glycol PPG, stirring at the speed of 1000-1500 rpm, and uniformly mixing;
s3, adding the catalyst A, the catalyst B, the silica gel, the cross-linking agent and water, stirring at 1500-2000 rpm, and uniformly mixing;
s4, adding TDI 80, stirring at a high speed of 2000-2500 rpm, uniformly mixing, pouring into a foaming tank for free foaming or continuously foaming by using a continuous foaming machine after mixing for 4-10S to obtain a polyurethane foaming semi-finished product;
s5, curing the sponge body for 12-48 h at room temperature to prepare the non-yellowing polyurethane sponge.
The beneficial effects of the invention are: the invention introduces the anti-yellowing auxiliary agent containing pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, bis-sebacate (2, 6-tetramethyl-4-piperidyl), 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazole-2-yl) phenol and tetraphenyl dipropylene glycol diphosphite, so as to prepare the polyurethane which is not easy to turn yellow and inhibit scorching in the foaming process.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to clearly and unequivocally define the scope of the present invention.
Example 1
The formula of the non-yellowing polyurethane sponge comprises the following raw materials in parts by weight:
the anti-yellowing auxiliary agent comprises pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, bissebacate (2, 6-tetramethyl-4-piperidyl), 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazole-2-yl) phenol and tetraphenylpropylene dipropylene glycol diphosphite, and the using amount of the auxiliary agent is 0.1-1% of the weight of the PPG polyether polyol.
Wherein: polyether polyol PPG is an organic polymer obtained by addition polymerization of an initiator (active hydrogen group-containing compound) with Ethylene Oxide (EO), propylene Oxide (PO), butylene Oxide (BO), etc. in the presence of a catalyst, and is a colorless, transparent, oily viscous liquid. The polyether polyol PPG3000 means that the molecular weight of PPG is about 3000.
TDI 80 refers to toluene diisocyanate (CAS NO. 26471-62-5), is colorless, transparent or yellowish flammable liquid, has strong pungent odor, and is used for manufacturing polyurethane foam, rubber, insulating paint, adhesive and the like.
Pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, irganox 1010 antioxidant is directly selected, has good compatibility, extraction resistance and low volatility, and can be used with other antioxidants and light stabilizers.
The bi-sebacate (2, 6-tetramethyl-4-piperidyl) directly selects a Tinuvin 770 DF light stabilizer, is a low-molecular-weight hindered amine light stabilizer, is suitable for application occasions with high requirements on light stability, particularly is added into a thick PP material to protect the surface light damage of the thick PP material, and has wide compatibility and easy dispersibility. The Tinuvin 770 DF light stabilizer has higher efficiency than the ultraviolet light stabilizer, can improve the heat resistance when used together with an antioxidant, inhibit scorching in the foaming process, and generate synergistic effect when used together with the ultraviolet light absorber to improve the light resistance effect.
4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazol-2-yl) phenol, directly selecting a Tinuvin 328 ultraviolet absorbent, wherein the Tinuvin 328 ultraviolet absorbent has characteristic strong absorption to ultraviolet rays at 300-400nm and almost does not absorb in a visible light region (> 400 nm); the compound is used together with other light stabilizers (Tinuvin 770 DF light stabilizer), antioxidants (Irganox 1010 antioxidant and JPP100 antioxidant) and other functional additives, and the Tinuvin 328 ultraviolet absorbent is used in combination with the Tinuvin 770 DF stabilizer, so that the compound synergistic effect is obvious.
The JPP100 antioxidant is directly selected as the tetraphenyl dipropylene glycol diphosphite, the JPP100 antioxidant is a high molecular weight phosphite antioxidant and is used as an auxiliary antioxidant, the capability of decomposing hydrogen through oxide is strong, and a good synergistic effect can be generated by combining the JPP100 antioxidant with the Irganox 1010 antioxidant and the Tinuvin 328 ultraviolet absorbent.
The cross-linking agent is trimethylolpropane.
The catalyst A is triethylene diamine.
The catalyst B is bis (dimethylaminoethyl) ether.
Example 2
A preparation method of the sponge comprises the following steps:
s1, weighing raw materials according to the weight parts of 100 parts of polyether polyol PPG3000, 1.0 part of catalyst A, 0.8 part of catalyst B, 1.0 part of silica gel, 2.0 parts of cross-linking agent, 40 parts of TDI 80, 0.2 part of Irganox 1010 antioxidant, 0.2 part of Tinuvin 770 DF light stabilizer, 0.2 part of Tinuvin 328 ultraviolet absorbent, 0.2 part of JPP100 antioxidant and 4 parts of water;
s2, pumping polyether polyol PPG3000 into a reaction kettle, stirring at the speed of 1000-1500 rpm, mixing Irganox 1010 antioxidant, tinuvin 770 DF light stabilizer, tinuvin 328 ultraviolet absorbent and JPP100 antioxidant into the reaction kettle through a feeding port of the reaction kettle in the stirring process, continuously stirring and uniformly mixing;
s3, adding triethylene diamine, bis (dimethylaminoethyl) ether, silica gel, trimethylolpropane and water into the reaction kettle, stirring at the speed of 1500-2000 rpm, and uniformly mixing;
s4, pumping TDI 80 into a reaction kettle, stirring at a high speed of 2000-2500 rpm, uniformly mixing, pouring into a foaming box for free foaming or continuously foaming by using a continuous foaming machine after mixing for 4-10S to obtain a polyurethane foaming semi-finished product;
s5, curing the sponge body for 12-48 h at room temperature to prepare the non-yellowing polyurethane sponge.
CO produced by a chemical reaction between the hydroxyl groups of water and the NCO groups of isocyanates 2 Foaming, wherein heat is continuously released in the foaming process, and the combination of the Tinuvin 770 DF light stabilizer, the Irganox 1010 antioxidant and the JPP100 antioxidant can improve the heat resistance and inhibit the occurrence of scorching in the foaming process; comprising pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, bissebacate (2, 6-tetramethyl-4-piperidyl), 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazol-2-yl) phenol andthe anti-yellowing assistant of tetraphenyl dipropylene glycol diphosphite ensures that the prepared polyurethane sponge is not easy to yellow, and the light fastness grade, the phenol yellowing resistance grade and the smoking resistance grade of the polyurethane sponge reach 4 grades and above.
Example 3
A preparation method of the sponge comprises the following steps:
s1, weighing raw materials according to the weight parts of 95 parts of polyether glycol PPG3000, 1.0 part of catalyst A, 0.8 part of catalyst B, 1.0 part of silica gel, 2.0 parts of cross-linking agent, 40 parts of TDI 80, 0.1 part of Irganox 1010 antioxidant, 0.1 part of Tinuvin 770 DF light stabilizer, 0.1 part of Tinuvin 328 ultraviolet absorbent, 0.1 part of JPP100 antioxidant and 3 parts of water;
s2, pumping polyether polyol PPG3000 into a reaction kettle, stirring at the speed of 1000-1500 rpm, mixing Irganox 1010 antioxidant, tinuvin 770 DF light stabilizer, tinuvin 328 ultraviolet absorbent and JPP100 antioxidant into the reaction kettle through a charging hole of the reaction kettle in the stirring process, continuously stirring and uniformly mixing;
s3, adding triethylene diamine, bis (dimethylaminoethyl) ether, silica gel, trimethylolpropane and water into the reaction kettle, stirring at the speed of 1500-2000 rpm, and uniformly mixing;
s4, pumping TDI 80 into a reaction kettle, stirring at a high speed of 2000-2500 rpm, uniformly mixing, pouring into a foaming box for free foaming or continuously foaming by using a continuous foaming machine after mixing for 4-10S to obtain a polyurethane foaming semi-finished product;
s5, curing the sponge body for 12-48 h at room temperature to prepare the non-yellowing polyurethane sponge.
Example 4
A preparation method of the sponge comprises the following steps:
s1, weighing raw materials according to the weight parts of 100 parts of polyether polyol PPG3000, 1.0 part of catalyst A, 0.8 part of catalyst B, 1.0 part of silica gel, 2.0 parts of cross-linking agent, 40 parts of TDI 80, 1.0 part of Irganox 1010 antioxidant, 1.0 part of Tinuvin 770 DF light stabilizer, 1.0 part of Tinuvin 328 ultraviolet absorbent, 1.0 part of JPP100 antioxidant and 5 parts of water;
s2, pumping polyether polyol PPG3000 into a reaction kettle, stirring at the speed of 1000-1500 rpm, mixing Irganox 1010 antioxidant, tinuvin 770 DF light stabilizer, tinuvin 328 ultraviolet absorbent and JPP100 antioxidant into the reaction kettle through a charging hole of the reaction kettle in the stirring process, continuously stirring and uniformly mixing;
s3, adding triethylene diamine, bis (dimethylaminoethyl) ether, silica gel, trimethylolpropane and water into the reaction kettle, stirring at the speed of 1500-2000 rpm, and uniformly mixing;
s4, pumping TDI 80 into a reaction kettle, stirring at a high speed of 2000-2500 rpm, uniformly mixing, pouring into a foaming box for free foaming or continuously foaming by using a continuous foaming machine after mixing for 4-10S to obtain a polyurethane foaming semi-finished product;
s5, curing the sponge body for 12-48 h at room temperature to prepare the non-yellowing polyurethane sponge.
The polyurethane sponge prepared in example 2 was subjected to light color fastness, phenol yellowing resistance and smoking color fastness tests, and the obtained light color fastness, phenol yellowing resistance and smoking resistance were all rated at 4 or above.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the present invention is not limited thereto, and any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (8)
1. The formula of the non-yellowing polyurethane sponge comprises the following raw materials in parts by weight:
2. the formulation of non-yellowing polyurethane sponge according to claim 1, wherein the anti-yellowing auxiliary comprises pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, bissebacate (2, 6-tetramethyl-4-piperidyl), 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazol-2-yl) phenol and tetraphenyldipropylene glycol diphosphite, each in an amount of 0.1 to 1% by weight of the polyether polyol PPG.
3. The formula of the non-yellowing polyurethane sponge according to claim 1, wherein the polyether polyol PPG is 95-100 parts, the catalyst A is 0.5-1.0 part, the catalyst B is 0.5-0.8 part, the silica gel is 0.5-1.0 part, the crosslinking agent is 1.5-2.5 parts, and the TDI 80 is 35-45 parts.
4. The formulation of the non-yellowing polyurethane sponge according to claim 3, wherein the polyether polyol PPG is 100 parts, the catalyst A is 1.0 part, the catalyst B is 0.8 part, the silica gel is 1.0 part, the crosslinking agent is 2.0 parts, and the TDI 80 is 40 parts.
5. The formulation of non-yellowing polyurethane sponge according to claim 1, wherein the polyether polyol PPG is polyether polyol PPG3000.
6. The formulation of non-yellowing polyurethane sponge according to claim 1, wherein the raw materials further comprise: 3-5 parts of water.
7. The formulation of non-yellowing polyurethane sponge according to any one of claims 1-6, wherein the catalyst A is triethylene diamine, the catalyst B is bis (dimethylaminoethyl) ether, and the crosslinking agent is trimethylolpropane.
8. A preparation method of a non-yellowing polyurethane sponge comprises the following steps:
s1, weighing raw materials according to the weight parts of 95-110 parts of PPG, 0.5-1.5 parts of A, 0.5-1.0 part of B, 0.5-1.5 parts of silica gel, 1.0-3.0 parts of a cross-linking agent, 30-50 parts of TDI, 3-5 parts of water, 0.1-1.0 part of pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 0.1-1.0 part of bis (sebacate) (2, 6-tetramethyl-4-piperidyl), 0.1-1.0 part of 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazole-2-yl) phenol and 0.1-1.0 part of tetraphenyl dipropylene glycol diphosphite;
s2, mixing pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, bissebacate (2, 6-tetramethyl-4-piperidyl), 4, 6-bis (1, 1-dimethylpropyl) -2- (2H-benzotriazole-2-yl) phenol and tetraphenylpropylene dipropylene glycol diphosphite into polyether glycol PPG, stirring at the speed of 1000-1500 rpm, and uniformly mixing;
s3, adding the catalyst A, the catalyst B, the silica gel, the cross-linking agent and water, stirring at 1500-2000 rpm, and uniformly mixing;
s4, adding TDI 80, stirring at a high speed of 2000-2500 rpm, uniformly mixing, pouring into a foaming box for free foaming or continuously foaming by using a continuous foaming machine after mixing for 4-10S to obtain a polyurethane foaming semi-finished product;
s5, curing the sponge body for 12-48 h at room temperature to prepare the non-yellowing polyurethane.
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| CN202211339625.1A CN115677968A (en) | 2022-10-28 | 2022-10-28 | Formula and preparation method of non-yellowing polyurethane sponge |
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| CN202211339625.1A CN115677968A (en) | 2022-10-28 | 2022-10-28 | Formula and preparation method of non-yellowing polyurethane sponge |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4289856A (en) * | 1978-11-14 | 1981-09-15 | The Toyo Rubber Industry Co., Ltd. | Process for preparing non-yellowing integral-skinned polyurethane foam using a polyol having a functionality of 4 to 8 |
| JP2006089562A (en) * | 2004-09-22 | 2006-04-06 | Kurabo Ind Ltd | Hardly yellowed flexible polyurethane foam and molded product obtained by molding the same |
| CN101775204A (en) * | 2010-01-21 | 2010-07-14 | 迪比喜化学贸易(上海)有限公司 | Composite antioxidant for polyurethane fiber |
| CN112063161A (en) * | 2020-08-22 | 2020-12-11 | 福建大方睡眠科技股份有限公司 | Antibacterial yellow-resistant environment-friendly bra cotton and preparation method thereof |
-
2022
- 2022-10-28 CN CN202211339625.1A patent/CN115677968A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4289856A (en) * | 1978-11-14 | 1981-09-15 | The Toyo Rubber Industry Co., Ltd. | Process for preparing non-yellowing integral-skinned polyurethane foam using a polyol having a functionality of 4 to 8 |
| US4289856B1 (en) * | 1978-11-14 | 1984-10-02 | ||
| JP2006089562A (en) * | 2004-09-22 | 2006-04-06 | Kurabo Ind Ltd | Hardly yellowed flexible polyurethane foam and molded product obtained by molding the same |
| CN101775204A (en) * | 2010-01-21 | 2010-07-14 | 迪比喜化学贸易(上海)有限公司 | Composite antioxidant for polyurethane fiber |
| CN112063161A (en) * | 2020-08-22 | 2020-12-11 | 福建大方睡眠科技股份有限公司 | Antibacterial yellow-resistant environment-friendly bra cotton and preparation method thereof |
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