CN103275289A - Environment-friendly flame-retardant self-skinning combined polyether and preparation method thereof - Google Patents
Environment-friendly flame-retardant self-skinning combined polyether and preparation method thereof Download PDFInfo
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- CN103275289A CN103275289A CN2013101707369A CN201310170736A CN103275289A CN 103275289 A CN103275289 A CN 103275289A CN 2013101707369 A CN2013101707369 A CN 2013101707369A CN 201310170736 A CN201310170736 A CN 201310170736A CN 103275289 A CN103275289 A CN 103275289A
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Abstract
The invention discloses environment-friendly flame-retardant self-skinning combined polyether and a preparation method of the combined polyether. The combined polyether comprises the following raw materials in parts by weight: 50-100 parts of polyether polyol, 0-50 parts of polymer polyol, 5-10 parts of chain extenders, 2-10 parts of crosslinking agents, 1.0-3.0 parts of foam stabilizers, 0.91-3.35 parts of catalysts, 0.3-1.5 parts of silicon oil, 0.2-0.7 part of water and 1-10 parts of flame retardants, wherein the total weight of polyether polyol and polymer polyol is 100 parts. The preparation method comprises the following steps of: sequentially adding weighed polyether polyol, polymer polyol, chain extenders, crosslinking agents, foam stabilizers, catalysts, water and flame retardants into a reaction kettle; and stirring for 45-60 minutes at constant temperature to obtain the environment-friendly flame-retardant self-skinning combined polyether. The preparation process is carried out at the constant temperature under constant pressure, is easy to operate, wide in processing range, stable in product quality, and low in odor, volatility of organic matters and production cost, and has certain flame retardant performance; and, three wastes are avoided.
Description
Technical field
The invention belongs to the urethane foam technical field, be specifically related to a kind of environment friendly flame-retardant from the skinning combined polyether.
Background technology
Along with the expansion of Domestic Automotive Industry production to materials demand, various type materials continue to bring out in recent years, and polyurethane synthetic material is exactly a kind of in the field of new.Advantages such as that polyurethane foamed material has is wear-resisting, low temperature resistant, oil resistant, damping property is good and quality is light have been applied to each corner of automobile by wide model, this material has become the emphasis that the automobile lightweight is selected for use.Traditional urethane plastic is to use fluorochlorohydrocarbon to make whipping agent.Fluorochlorohydrocarbon has destruction to the ozonosphere of atmosphere, and shortcoming such as finished product smell weight, poor fire is eliminated gradually.Present homemade polyurethane production enterprise has developed a lot of fluorochlorohydrocarbon substitutes as whipping agent, and full water foamedly replaced the HCFC141b system basically from the skinning combined polyether, accounted for from 80% of skinning combined polyether, but still the cementability that exists foam and base material is poor, poor stability, and epidermis is thin, poor fire, job efficiency is low, can't satisfy new shortcomings such as automotive trim material environmental requirement, thereby limit the promotion and application of full water foamed polyurethane foam on medium-to-high grade automobile.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, and provide a kind of good fluidity, the processing latitude is big, the epidermis densification, be difficult for peeling, slaking is fast, the demoulding is fast, stability in storage is good, environmental protection index meets German VDA standard and environment friendly flame-retardant with certain flame retardant resistance from skinning combined polyether and preparation method.
A kind of environment friendly flame-retardant of the present invention is from the skinning combined polyether, and it can be made into environment friendly flame-retardant polyurethane integral skin foam plastics as a kind of A component with the B component, and described combined polyether is made up of following raw material according to the weight part meter:
Polyether glycol: 50～100 parts;
Polymer polyatomic alcohol: 0～50 part;
Chainextender: 5～10 parts;
Linking agent: 2～10 parts;
1.0～3.0 parts of suds-stabilizing agents;
Catalyzer: 0.91～3.35 part;
Silicone oil: 0.3～1.5 part;
Water: 0.2～0.7 part;
Fire retardant: 1～10 part;
Wherein: polyether glycol and polymer polyatomic alcohol amount to 100 parts.
Described polyether glycol is initiator with glycerine, and propylene oxide and epoxyethane ring-expansion polymerization form, and functionality is 3, and number-average molecular weight is 6000; 2～40 parts of described polymer polyatomic alcohols, it is to be basic polyethers with polyether triol, is polymerized solid content 30 with the styrene-acrylonitrile mix monomer; Described fire retardant is alkyl chloride Quito poly phosphate; Described catalyzer is in A component total weight parts, by catalyst I: 0.1～0.8 part, catalyst I I:0.5～1.5 part, catalyst I II:0.3～1.0 part, catalyst I V:0.01～0.05 part composition.
Described chainextender is ethylene glycol, and functionality is 2, molecular weight 62; Described linking agent is polyether glycol MN-1000; Described suds-stabilizing agent is the silicone tensio-active agent; Described fire retardant is alkyl chloride Quito poly phosphate; Described catalyzer is in A component total weight parts, by catalyst I: 0.1～0.8 part, catalyst I I:0.5～1.5 part, catalyst I II:0.3～1.0 part, catalyst I V:0.01～0.05 part composition.
Described catalyst I is the derivative of two (dimethylaminoethyl) ethers; Described catalyst I I is the non-balance catalyzer that distributes; Described catalyst I II is gel catalyst; Described catalyst I V is a kind of organotin.
A kind of according to the preparation method of above-mentioned environment friendly flame-retardant from the skinning combined polyether, this preparation method is: with load weighted polyether glycol, polymer polyatomic alcohol, chainextender, linking agent, suds-stabilizing agent, catalyzer, water, fire retardant, join in the reactor successively, stir at normal temperatures down and stirred 45 minutes～60 minutes, namely obtain environment friendly flame-retardant from the skinning combined polyether.
With this combined polyether and modification MDI, namely the B component mixes by the mass ratio of A/B=100:48～55, namely can be made into the polyurethane integral skin foam plastics.
The B component is the derivative liquefied mdi of isocyanic ester, and another name modification MDI adopts Hensel to step chemical industry trade (Shanghai) Co., Ltd. and produces trade mark SUPRASEC2020.
Applying of A component of the present invention, can thoroughly eliminate Ozone Depleting Substances and reach German VDA standard at smell, TVOC, atomizing, benzene,toluene,xylene, ethylbenzene, formaldehyde etc., make polyurethane industrial become real cleaning, safe and effective industry, accelerate the process that China's fluorochlorohydrocarbon replaces, promote China's polyurethane industrial to catch up with international most advanced level.Adopt combined polyether of the present invention and modification MDI to prepare foam, production technique is at normal temperature, carries out under the normal pressure, and easy to operate, work range is big, has certain flame retardant resistance, and smell is low, and organic volatilization is low, the no three wastes, and constant product quality, production cost is low.
The invention has the advantages that to take full advantage of water as the advantage of whipping agent, by regulating catalyst system, overcome its deficiency, thereby obtain to have certain flame retardant resistance, environmental protection index reaches German VDA standard, the polyurethane integral skin foam plastics of fast demoulding.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited only to this.
A kind of environment friendly flame-retardant of the present invention is from the skinning combined polyether, and it can be made into environment friendly flame-retardant polyurethane integral skin foam plastics as a kind of A component with the B component, and described combined polyether is made up of following raw material according to the weight part meter:
Polyether glycol: 50～100 parts;
Polymer polyatomic alcohol: 0～50 part;
Chainextender: 5～10 parts;
Linking agent: 2～10 parts;
1.0～3.0 parts of suds-stabilizing agents;
Catalyzer: 0.91～3.35 part;
Silicone oil: 0.3～1.5 part;
Water (whipping agent): 0.2～0.7 part;
Fire retardant: 1～10 part;
Wherein: polyether glycol and polymer polyatomic alcohol amount to 100 parts.
Described polyether glycol is initiator with glycerine, and propylene oxide and epoxyethane ring-expansion polymerization form, and functionality is 3, and number-average molecular weight is 6000, adopts Shandong Lanxing Dongda Chemical Co.,Ltd to produce, and the trade mark is EP-3600; 2～40 parts of described polymer polyatomic alcohols, it is to be basic polyethers with polyether triol, is polymerized solid content 30 with the styrene-acrylonitrile mix monomer; Described fire retardant is alkyl chloride Quito poly phosphate; Described catalyzer is in A component total weight parts, by catalyst I: 0.1～0.8 part, catalyst I I:0.5～1.5 part, catalyst I II:0.3～1.0 part, catalyst I V:0.01～0.05 part composition.
Described chainextender is ethylene glycol, and functionality is 2, molecular weight 62; Described linking agent is the polyether glycol MN-1000 of Shandong Lanxing Dongda Chemical Co.,Ltd; Suds-stabilizing agent is the silicone tensio-active agent, can adopt air products company to produce, and the trade mark is Dabco DC2525; Described fire retardant is alkyl chloride Quito poly phosphate, can adopt Zhejiang Province Wansheng Chemical Co., Ltd to produce trade mark FR-504L; Described catalyzer is in A component total weight parts, by catalyst I: 0.1～0.8 part, catalyst I I:0.5～1.5 part, catalyst I II:0.3～1.0 part, catalyst I V:0.01～0.05 part composition.
Described catalyst I is the derivative of two (dimethylaminoethyl) ethers, can adopt Hensel to step chemical industry trade (Shanghai) Co., Ltd. and produce trade mark ZF-10; Described catalyst I I is the non-balance catalyzer that distributes, and can adopt air products company to produce, and the trade mark is Dabco NE210 or Dabco NE600; Described catalyst I II is gel catalyst, can adopt air products company to produce, and the trade mark is Dabco NE500 or Dabco NE1070; Described catalyst I V is a kind of organotin, adopts German NITRIOL company to produce, and the trade mark is T120.
A kind of according to the preparation method of above-mentioned environment friendly flame-retardant from the skinning combined polyether, this preparation method is: with load weighted polyether glycol, polymer polyatomic alcohol, chainextender, linking agent, suds-stabilizing agent, catalyzer, water, fire retardant, join in the reactor successively, stir at normal temperatures down and stirred 45 minutes～60 minutes, namely obtain environment friendly flame-retardant from the skinning combined polyether.
With this combined polyether and modification MDI, namely the B component mixes by the mass ratio of A/B=100:48～55, namely can be made into the polyurethane integral skin foam plastics.
The B component is the derivative liquefied mdi of isocyanic ester, and another name modification MDI adopts Hensel to step chemical industry trade (Shanghai) Co., Ltd. and produces trade mark SUPRASEC2020.
Embodiment:
Embodiment 1: with 50 parts of load weighted polyether glycols, 50 parts of polymer polyatomic alcohols, 5 parts of chainextenders, 2 parts of linking agents, 1 part of suds-stabilizing agent, catalyst I: 0.1 part, catalyst I I:0.5 part, catalyst I II:0.3 part, catalyst I V:0.01 part, 0.2 part in water, 1 part of fire retardant, join in the reactor successively, stir at normal temperatures down and stirred 45 minutes, namely obtain full water from the skinning combined polyether, it is the A component, with this combined polyether and modification MDI, being the B component mixes by the mass ratio of A/B=100:48, namely can be made into the polyurethane integral skin foam plastics.
Embodiment 2: with 100 parts of load weighted polyether glycols, 0 part of polymer polyatomic alcohol, 10 parts of chainextenders, 10 parts of linking agents, 3 parts of suds-stabilizing agents, catalyst I: 0.8 part, catalyst I I:1.5 part, catalyst I II:1.0 part, catalyst I V:0.05 part, 0.7 part in water, 10 parts of fire retardants, join in the reactor successively, stir at normal temperatures down and stirred 60 minutes, namely obtain full water from the skinning combined polyether, it is the A component, with this combined polyether and modification MDI, being the B component mixes by the mass ratio of A/B=100:55, namely can be made into the polyurethane integral skin foam plastics.
Embodiment 3: with 75 parts of load weighted polyether glycols, 25 parts of polymer polyatomic alcohols, 7.5 parts of chainextenders, 6 parts of linking agents, 2 parts of suds-stabilizing agents, catalyst I: 4.5 parts, catalyst I I:1.0 part, catalyst I II:6.5 part, catalyst I V:0.03 part, water 0.45,5 parts of fire retardants, join in the reactor successively, stir at normal temperatures down and stirred 50 minutes, namely obtain full water from the skinning combined polyether, it is the A component, with this combined polyether and modification MDI, being the B component mixes by the mass ratio of A/B=100:52, namely can be made into the polyurethane integral skin foam plastics.
The integral skin foam plastics that adopt the inventive method to produce can reach following index:
The bearing circle goods are apparent: epidermis densification, no skin effect phenomenon;
Freely steep density: 145～195kg/m
3
Molding global density: 330～370kg/m
3
Hardness (Shore A) 55～75
Tear strength: 8～15N/mm
Ultimate compression strength: 2.5～4Mpa
Smoke density grade (SDR) :≤75
Oxygen index (OI): 〉=22
Burning length :≤70mm/min
TVOC(ugC/g)： ≤50
Atomizing (mg) :≤3
Smell :≤3.5
Toluene (ug/g) :≤5
Dimethylbenzene (ug/g) :≤15
Formaldehyde (ug/g) :≤10
Ethylbenzene (ug/g) :≤15
Benzene (ug/g) :≤5
The present invention also comprises the embodiment that is described in table 1 below, they are preparation as follows all: with load weighted polyether glycol, polymer polyatomic alcohol, chainextender, linking agent, suds-stabilizing agent, catalyzer, water, fire retardant, join in the reactor successively, stir at normal temperatures down and stirred 45 minutes～60 minutes, namely obtain full water from the skinning combined polyether, it is the A component, with this combined polyether and modification MDI, being the B component mixes by the mass ratio of A/B=100:48～55, namely can be made into the polyurethane integral skin foam plastics.
Table 1
Claims (5)
1. an environment friendly flame-retardant is from the skinning combined polyether, and it can be made into environment friendly flame-retardant polyurethane integral skin foam plastics as a kind of A component with the B component, it is characterized in that described combined polyether according to the weight part meter, is made up of following raw material:
Polyether glycol: 50～100 parts;
Polymer polyatomic alcohol: 0～50 part;
Chainextender: 5～10 parts;
Linking agent: 2～10 parts;
1.0～3.0 parts of suds-stabilizing agents;
Catalyzer: 0.91～3.35 part;
Silicone oil: 0.3～1.5 part;
Water: 0.2～0.7 part;
Fire retardant: 1～10 part;
Wherein: polyether glycol and polymer polyatomic alcohol amount to 100 parts.
2. environment friendly flame-retardant according to claim 1 is characterized in that from the skinning combined polyether described polyether glycol is initiator with glycerine, and propylene oxide and epoxyethane ring-expansion polymerization form, and functionality is 3, and number-average molecular weight is 6000; 2～40 parts of described polymer polyatomic alcohols, it is to be basic polyethers with polyether triol, is polymerized solid content 30 with the styrene-acrylonitrile mix monomer; Described fire retardant is alkyl chloride Quito poly phosphate; Described catalyzer is in A component total weight parts, by catalyst I: 0.1～0.8 part, catalyst I I:0.5～1.5 part, catalyst I II:0.3～1.0 part, catalyst I V:0.01～0.05 part composition.
3. environment friendly flame-retardant according to claim 1 is characterized in that from the skinning combined polyether described chainextender is ethylene glycol, and functionality is 2, molecular weight 62; Described linking agent is polyether glycol MN-1000; Described suds-stabilizing agent is the silicone tensio-active agent; Described fire retardant is alkyl chloride Quito poly phosphate; Described catalyzer is in A component total weight parts, by catalyst I: 0.1～0.8 part, catalyst I I:0.5～1.5 part, catalyst I II:0.3～1.0 part, catalyst I V:0.01～0.05 part composition.
According to claim 2 or 3 described environment friendly flame-retardants from the skinning combined polyether, it is characterized in that described catalyst I is the derivative of two (dimethylaminoethyl) ethers; Described catalyst I I is the non-balance catalyzer that distributes; Described catalyst I II is gel catalyst; Described catalyst I V is a kind of organotin.
5. according to claim 1 or 2 or the 3 or 4 described environment friendly flame-retardants preparation method from the skinning combined polyether, it is characterized in that this preparation method is: with load weighted polyether glycol, polymer polyatomic alcohol, chainextender, linking agent, suds-stabilizing agent, catalyzer, water, fire retardant, join in the reactor successively, stir at normal temperatures down and stirred 45 minutes～60 minutes, namely obtain environment friendly flame-retardant from the skinning combined polyether.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211892A (en) * | 2014-08-05 | 2014-12-17 | 滁州宝瑞橡胶制品有限公司 | Low-density integral skin used for seat |
| CN103641979B (en) * | 2013-12-09 | 2015-12-02 | 山东一诺威聚氨酯股份有限公司 | Mine polyurethane is from antiskinning composition and preparation method thereof |
| CN105482064A (en) * | 2015-12-08 | 2016-04-13 | 佛山市雅洁源科技股份有限公司 | Environmentally friendly nontoxic foam |
| CN106117491A (en) * | 2016-07-25 | 2016-11-16 | 重庆钱珑新科技有限公司 | Complete water base organic foam material of polyurethane and preparation method thereof |
| CN109517137A (en) * | 2018-10-09 | 2019-03-26 | 杭州康诚汽车附件有限公司 | Preparation method of the operating passenger car from skinning combination material |
| CN109971161A (en) * | 2019-03-26 | 2019-07-05 | 上海馨源新材料科技有限公司 | A kind of low smell automobile polyurethane material and preparation method thereof |
| CN111072896A (en) * | 2019-12-27 | 2020-04-28 | 江苏世丰新材料有限公司 | Low-odor flame-retardant polyurethane foam material for vehicle interior decoration and preparation method thereof |
| CN116284657A (en) * | 2023-02-06 | 2023-06-23 | 上海聚泽优汽车内饰件材料有限公司 | Formula of self-skinning product for automobile |
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| CN101602839A (en) * | 2008-06-10 | 2009-12-16 | 上海合达聚合物科技有限公司 | A kind of integral skin polyurethane-urea composition, its preparation method and application |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641979B (en) * | 2013-12-09 | 2015-12-02 | 山东一诺威聚氨酯股份有限公司 | Mine polyurethane is from antiskinning composition and preparation method thereof |
| CN104211892A (en) * | 2014-08-05 | 2014-12-17 | 滁州宝瑞橡胶制品有限公司 | Low-density integral skin used for seat |
| CN105482064A (en) * | 2015-12-08 | 2016-04-13 | 佛山市雅洁源科技股份有限公司 | Environmentally friendly nontoxic foam |
| CN106117491A (en) * | 2016-07-25 | 2016-11-16 | 重庆钱珑新科技有限公司 | Complete water base organic foam material of polyurethane and preparation method thereof |
| CN109517137A (en) * | 2018-10-09 | 2019-03-26 | 杭州康诚汽车附件有限公司 | Preparation method of the operating passenger car from skinning combination material |
| CN109971161A (en) * | 2019-03-26 | 2019-07-05 | 上海馨源新材料科技有限公司 | A kind of low smell automobile polyurethane material and preparation method thereof |
| CN111072896A (en) * | 2019-12-27 | 2020-04-28 | 江苏世丰新材料有限公司 | Low-odor flame-retardant polyurethane foam material for vehicle interior decoration and preparation method thereof |
| CN116284657A (en) * | 2023-02-06 | 2023-06-23 | 上海聚泽优汽车内饰件材料有限公司 | Formula of self-skinning product for automobile |
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