CN1133853A - Fluorine-free polyurethane foamed plastics - Google Patents
Fluorine-free polyurethane foamed plastics Download PDFInfo
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- CN1133853A CN1133853A CN 96100797 CN96100797A CN1133853A CN 1133853 A CN1133853 A CN 1133853A CN 96100797 CN96100797 CN 96100797 CN 96100797 A CN96100797 A CN 96100797A CN 1133853 A CN1133853 A CN 1133853A
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Abstract
A hard fluorine-free polyurethane foam plastics as ideal insulating material of refrigerator, cold storage, or pipeline are prepared through the reaction of aliphatic oil with polyol at a certain temp in the presence of alkaline catalyst to synthesize high-branched hydroxy-terminated polyester-polyether polyol and the reaction of the obtained polyester-polyether polyol with isocyanate in the presence of catalyst, foamer and homogenizer, and features protection for chemosphere and low cost.
Description
The present invention relates to a kind of floride-free polyurethane porous plastics, referring in particular to a kind of is the no-freon polyurethane hard foam plastic of raw material with the high degree of branching, hydroxyl telechelic polyester-polyether glycol.
The polyurethane porous plastics is novel synthetic materials, is called urethane foam again.It is to be main raw material by isocyanic ester with the vibrin that contains hydroxyl (OH), adds subsidiary material such as catalyzer, whipping agent, suds-stabilizing agent, and the chemical reaction moulding takes place.
Polyurethane rigid foam plastic has good heat-insulating property (being that thermal conductivity is low) and stronger structural strength, has that unit weight is low, sound insulation, shockproof, oil resistant, acidproof, alkaline-resisting, characteristics such as water-intake rate is low, the room temperature chemical stability is good.
The hard polyurethane foam speed of development is very fast, has been widely used in fields such as building, communications and transportation, petrochemical complex, food storage and home appliances.Because processing is simple and have a good Cryo Heat Insulation, partition plate, roof and the floor insulation layer material etc. of the lagging material of refrigerator, refrigerator chamber, freezer and oil liquefied gas and chemical industry refrigerating apparatus, piping insulation, building industry Shen have been used for as the unique low-temperature material.
Because raw material sources are abundant, have fast foaming solidified characteristics and good bounding force, but therefore in-situ spraying, cast-in-situ or pre-formed, construction is simple, long service life, and have anticorrosion and Fire retardance is present insulation, cold insulation, energy-conservation ideal material.
The making method of traditional porous plastics is to be starting material with the polyethers, is whipping agent with F11 (3 fluoro-methyl chloride), owing to will discharge a large amount of fluorine Lyons gas in the bubble process Shen of hardening, atmospheric ozone layer is destroyed, and the World Health Organization has proposed floride-free requirement.The 94 years China and the World Health Organization give ample rewards to the half fluorine raw material preparing polyurethane heat insulation material that Liming chemical Inst of China the Ministry of Chemical Industry cooperates with Shenyang Petroleum-Chemial Plant to work out, at the protection atmospheric ozone layer, reduce and stepping a gratifying step aspect the environment for human survival destruction.But because the starting material of this half fluorine are to utilize modified phenolic resins to remove modification Z1050 polyethers, make it to dissolve a certain amount of chemical foaming agent, viscosity ratio Z1050 reduces, but its viscosity remains the prerequisite that influences it and enlarge use, that is to say, the starting material of half fluorine and technology can't solve floride-free every technical barrier, and therefore subtracting the fluorine amount has only 50%, does not far reach the requirement of the World Health Organization.At present, domestic each refrigerator factory adopts the 141B (a fluorine ethylene dichloride) of U.S.'s development to replace F11 in succession, though the fluoro-gas that 141B discharges contains fluorine than F11 much less in the molecular formula of 141B, still there is the composition of fluorine in its steam in the bubble process of hardening.
The purpose of this invention is to provide a kind of no-freon polyurethane hard foam plastic, it adopts floride-free polymkeric substance is raw material, add floride-free whipping agent, not only solved in the fluorine-containing and foaming process of the raw material of existing lagging material and discharge the problem of fluorine, and can guarantee the quality of foam article.
The object of the present invention is achieved like this:
Fluorine-free polyurethane foamed plastics is to be raw material with the high degree of branching, hydroxyl telechelic polyester-polyether glycol, the wherein high degree of branching, hydroxyl telechelic polyester-polyether glycol are to adopt aliphatics grease and polyvalent alcohol, at a certain temperature, reaction is synthetic in the presence of basic catalyst, its processing parameter: temperature of reaction is 80～240 ℃, reaction times is 2～8 hours, and reaction pressure is 0～0.4mpa, gets with the mixed of polyether glycol through the propylene oxide grafting or in the presence of coupling agent again; Institute's synthetic polyester-polyether glycol generates fluorine-free polyurethane foamed plastics with isocyanate reaction in the presence of catalyzer, chemical foaming agent, foam stabilizer.
The present invention adopts following three kinds of prescriptions:
(1) A component: 100 parts of polyester-polyether glycols
2～5 parts of foam stabilizers
3～5 parts of whipping agents
Catalyzer: 1.0～3.0 parts of triethylene diamines
0～0.5 part of organotin
B component: isocyanate index 1.0～2.0
(2) A component: 100 parts of polyester-polyether glycols
2～5 parts of foam stabilizers
3～5 parts of whipping agents
Catalyzer: 0.5～1.5 part of potassium oleate
1.5～4.5 parts of catalyst for trimerization
B component: isocyanate index 1.0～2.0
(3) A component: 100 parts of polyester-polyether glycols
2～5 parts of foam stabilizers
3～5 parts of whipping agents
Catalyzer: 2～5 parts of triethylene diamines
0.5～1 part of dimethyl ethylenimine
B component: isocyanate index 1.0～2.0
It is starting material that the present invention has adopted a kind of high degree of branching, hydroxyl telechelic polyester-polyether glycol, and its main chain is to be that aliphatics grease and polyvalent alcohol esterification obtain by containing ester bond.Ether-containing key is by polyvalent alcohol and propylene oxide ring-opening polymerization and get, or in the presence of coupling agent, make and utilize aliphatics grease and polyvalent alcohol to connect to macromole with polyether monomer again by the polyester department that esterification obtains, therefore thereby introduce enough ehter bonds, can make intensity that the rigid foam that utilizes this polyester-polyethers preparation not only possessed polyester article simultaneously but also possess the activity of polyethers.
Chemical foaming agent among the present invention can be a water.
Polyester-polyether glycol of the present invention can obtain and chemical foaming agent H thus owing to the existence of ester bond
2The intermiscibility of O, with the intermiscibility and the long storage of other auxiliary agents, and the long-chain section that q.s is arranged in molecular structure.Therefore,, in foaming process, there is the product of the short hard segment of a large amount of biurets to produce, can not influences the snappiness of foam article even whipping agent adopts water.
Because in polyester-polyether glycol enough ehter bonds are arranged, it will guarantee its raw-material activity thus, thereby reach the room temperature foaming.
Reaction principle of the present invention is as follows:
(1) hydroxy-containing compounds (as polyethers etc.) and isocyanate reaction generate carbamate:
This reaction is the basic chemical reaction of each urethane of preparation, outside the characteristics of dehydrogenation atom transfer, does not have small molecule by-product to separate out in the reaction.
(2) isocyanic ester and water reaction (foamable reaction):
Isocyanic ester and water reaction generate unsettled carboxylamine, resolve into amine immediately and emit carbonic acid gas simultaneously
(3) isocyanic ester and amine reaction:
The reaction back generates the derivative of urea.And then, finally generate biuret with certain speed and isocyanate reaction.
(4) isocyanic ester and urethane reaction:
Under comparatively high temps, isocyanic ester and carboxylamine reaction generate allophanate.
(5) derivatives reaction of isocyanic ester and urea:
The derivatives reaction of isocyanic ester and urea generates biuret.
(6) with the hydroxy acid reaction:
The reaction of isocyanic ester and hydroxy acid and with the water reacting phase seemingly, addition reaction before this forms sour acid amides, meets the heat back and decomposes and emit carbonic acid gas.
(7) with the acid amides reaction:
(8) the own self-polymeric reaction of isocyanic ester:
With the hand dropping is example, and the making method of fluorine-free polyurethane foamed plastics comprises the steps:
(1) produces qualified mould according to construction requirement;
(2) demoulding: adopt release materials commonly used;
(3) construction technology: A component material is put into container according to a certain ratio with B component material mix, use electronic stirring that compound is stirred;
(4) temperature control:
Envrionment temperature: more than 20 ℃
Material temperature: 25～30 ℃ of isocyanic ester
20～25 ℃ of combined polyethers
40～60 ℃ of die temperatures
The general pouring foaming time was controlled at 35～45 seconds, should be controlled at set time 60～100 seconds.
Advantage of the present invention is: no matter be all not conform in starting material or the whipping agent fluorine is arranged; therefore in foaming process, can not discharge fluorine Lyons; reach floride-free requirement; protected atmospheric ozone layer; protected existent environment of people, manufacture craft is simple simultaneously, has shortened technical process; having reduced cost, is the lagging material of a kind of ideal freezer, pipeline etc.
The embodiment of three kinds of prescriptions is provided below:
In following examples, the raw material of fluorine-free polyurethane foamed plastics is a kind of high degree of branching, hydroxyl telechelic polyester-polyether glycol, adopts aliphatics grease and polyol reaction.
Wherein the aliphatics grease can be oleum lini or castor oil.Polyvalent alcohol can be starch and derivative, various polyol compound or various terminal hydroxy group ethers.Chemical foaming agent is a water.
Embodiment 1:
Select for use prescription to be:
A component: 100 parts of polyester-polyether glycols
2 parts of foam stabilizers
4 parts of whipping agents
Catalyzer: 1.0 parts of triethylene diamines
0.2 part of B component of organotin: isocyanate index 1.0～2.0
Embodiment 2:
Select for use prescription to be:
A component: 100 parts of polyester-polyether glycols
5 parts of foam stabilizers
4 parts of whipping agents
Catalyzer: 0.8 part of potassium oleate
4.0 parts of catalyst for trimerization
B component: isocyanate index 1.0～2.0
Embodiment 3:
Select for use prescription to be:
A component: 100 parts of polyester-polyether glycols
4 parts of foam stabilizers
5 parts of whipping agents
Catalyzer: 5 parts of triethylene diamines
0.6 part of B component of dimethyl ethylenimine: isocyanate index 1.0～2.0
Claims (5)
1, a kind of fluorine-free polyurethane foamed plastics is to be raw material with the high degree of branching, hydroxyl telechelic polyester-polyether glycol, it is characterized in that:
(1) the described high degree of branching, hydroxyl telechelic polyester-polyether glycol are to adopt aliphatics grease and polyvalent alcohol, at a certain temperature, reaction is synthetic in the presence of basic catalyst, its processing parameter is: temperature of reaction: 80～240 ℃, reaction times: 2～8 hours, reaction pressure: 0～0.4mpa, grafting propylene oxide or in the presence of coupling agent, mix again with polyether glycol;
(2) institute's synthetic polyester-polyether glycol generates fluorine-free polyurethane foamed plastics with isocyanate reaction in the presence of catalyzer, chemical foaming agent, foam stabilizer.
2, fluorine-free polyurethane foamed plastics according to claim 1 is characterized in that adopting following three kinds of prescriptions:
(1) A component: 100 parts of polyester-polyether glycols
2～5 parts of foam stabilizers
3～5 parts of whipping agents
Catalyzer: 1.0～3.0 parts of triethylene diamines
0～0.5 part of organotin
B component: isocyanate index 1.0～2.0
(2) A component: 100 parts of polyester-polyether glycols
2～5 parts of foam stabilizers
3～5 parts of whipping agents
Catalyzer: 0.5～1.5 part of potassium oleate
1.5～4.5 parts of catalyst for trimerization
B component: isocyanate index 1.0～2.0
(3) A component: 100 parts of polyester-polyether glycols
2～5 parts of foam stabilizers
3～5 parts of whipping agents
Catalyzer: 2～5 parts of triethylene diamines
0.5～1 part of dimethyl ethylenimine
B component: isocyanate index 1.0～2.0
3, fluorine-free polyurethane foamed plastics according to claim 1 is characterized in that described chemical foaming agent is a water.
4, fluorine-free polyurethane foamed plastics according to claim 1 is characterized in that described aliphatics grease can be oleum lini or castor oil.
5, fluorine-free polyurethane foamed plastics according to claim 1 is characterized in that described polyvalent alcohol can be starch and derivative, various polyol compound or various terminal hydroxy group ethers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100797A CN1077115C (en) | 1996-02-12 | 1996-02-12 | Fluorine-free polyurethane foamed plastics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100797A CN1077115C (en) | 1996-02-12 | 1996-02-12 | Fluorine-free polyurethane foamed plastics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1133853A true CN1133853A (en) | 1996-10-23 |
| CN1077115C CN1077115C (en) | 2002-01-02 |
Family
ID=5116746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96100797A Expired - Fee Related CN1077115C (en) | 1996-02-12 | 1996-02-12 | Fluorine-free polyurethane foamed plastics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1077115C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062997B (en) * | 2006-04-30 | 2011-01-12 | 王爱华 | Vegetable oil polyether polyatomic alcohol duromer polyurethane foam plastic pouring material |
| CN102040725A (en) * | 2010-11-09 | 2011-05-04 | 烟台德邦电子材料有限公司 | Flame retardant polyurethane resin and preparation method thereof and flame retardant polyurethane conformal coating |
| CN110003440A (en) * | 2019-04-24 | 2019-07-12 | 东莞市腾崴塑胶制品有限公司 | A kind of polyester ether sponge and preparation method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654507B (en) * | 2009-09-30 | 2011-09-28 | 大庆油田有限责任公司 | Low temperature high strength fluorine-free polyurethane foam heat insulation material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51128A (en) * | 1974-06-19 | 1976-01-05 | Mitsuharu Yamaguchi | |
| JPS559144A (en) * | 1978-07-07 | 1980-01-23 | Tokyo Keiki Co Ltd | Data processing system |
| JPS6395216A (en) * | 1986-10-11 | 1988-04-26 | Kurimoto Iron Works Ltd | Iron pipe coated with solventless two-pack type urethane coating material composition |
| JP3032849B2 (en) * | 1991-06-24 | 2000-04-17 | 光洋精工株式会社 | Power steering device |
| EP0672697A1 (en) * | 1994-03-17 | 1995-09-20 | Bayer Ag | Process for the preparation of rigid foams having urethane, urea and biuret groups and their use |
-
1996
- 1996-02-12 CN CN96100797A patent/CN1077115C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062997B (en) * | 2006-04-30 | 2011-01-12 | 王爱华 | Vegetable oil polyether polyatomic alcohol duromer polyurethane foam plastic pouring material |
| CN102040725A (en) * | 2010-11-09 | 2011-05-04 | 烟台德邦电子材料有限公司 | Flame retardant polyurethane resin and preparation method thereof and flame retardant polyurethane conformal coating |
| CN102040725B (en) * | 2010-11-09 | 2012-11-21 | 烟台德邦科技有限公司 | Flame retardant polyurethane resin and preparation method thereof and flame retardant polyurethane conformal coating |
| CN110003440A (en) * | 2019-04-24 | 2019-07-12 | 东莞市腾崴塑胶制品有限公司 | A kind of polyester ether sponge and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1077115C (en) | 2002-01-02 |
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