CN101358030B - Method for preparing high performance urethane elastomer for thermal barrier coating - Google Patents
Method for preparing high performance urethane elastomer for thermal barrier coating Download PDFInfo
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- CN101358030B CN101358030B CN2008101509047A CN200810150904A CN101358030B CN 101358030 B CN101358030 B CN 101358030B CN 2008101509047 A CN2008101509047 A CN 2008101509047A CN 200810150904 A CN200810150904 A CN 200810150904A CN 101358030 B CN101358030 B CN 101358030B
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Abstract
The invention provides a preparation method of a thermal insulation coating high-performance polyurethane elastomer. After the reaction of terminal hydroxyl polybutadiene liquid rubber and polyisocyanate, polyurethane is added for reaction for 3 to 4.5 hours at 85 to 90 DEG C to produce isocyanate-terminated prepolymer; a certain amount of heat insulating filler is added in the prepolymer and is mixed evenly to produce component A; chain extender, antioxidant, curing agent and solvent are mixed evenly according to a certain portion to produce component B; the component A and the component B with the weight portion of 3: 1 to 6: 1 are mixed, stirred evenly, cured at room temperature to produce the thermal insulation coating high-performance polyurethane elastomer. The process of the invention used to synthesize the thermal insulation coating high-performance polyurethane elastomer is more reasonable, the product has higher quality and better comprehensive properties. The test date shows that the tensile strength is 3.50 to 5.80MPa, the elongation at break is more than 220 percent, the bond strength is more than 10.0MPa, the glass transition temperature is less than 60 DEG C below zero, the solidification shrinkage rate is less than 0.1 percent. The product is mainly applicable to aerospace industry.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of preparation of high-performance polyurethane elastomer, relate in particular to of the preparation of a kind of heat insulating coat, be mainly used in fields such as being applied to aerospace with high-performance polyurethane elastomer.
Background technology
When flyer passes dense atmosphere with high speed; because its compression and friction to ambient air; can produce a large amount of heat energy; impel the flyer housing to deform; thereby influenced the performance of flyer, so need a kind of polyurethane material wear-resisting, high temperature resistant and that flyer base material adhesive property is good flyer to be protected as coating.Require to have high-low temperature resistant, rub resistance as the film forming matter of heat insulating coat, good springiness, the cured article shrinking percentage is little, the body mechanical property is good, with the characteristics such as strong adhesion of ground.Both at home and abroad materials such as silicone resin, urethane that adopt more, best with the urethane performance.Domestic isocyanate terminated base polyurethane prepolymer mainly contains the polyethers performed polymer that obtains with oligomer polyol (as PPG) and polyisocyanates; By polytetrahydrofuran diol (PTMG) and the isocyanate terminated PTMG performed polymer of tolylene diisocyanate reaction synthetic; With PTMG (PTMG) and the isocyanate terminated PTMG performed polymer of tolylene diisocyanate reaction synthetic; With hydroxy-terminated polybutadienes (HTPB) as raw material, the isocyanate terminated basic polyhutadiene performed polymer of preparation; With tolylene diisocyanate (TDI) and end hydroxy butadiene-styrene synthetic butylbenzene hydroxyl base polyurethane prepolymer for use as; With isocyanate-terminated base polyurethane prepolymer for use as; The straight chain organosilicon (PDMS) and the dimethylol propionic acid (DMPA) that contain hydroxyethyl with two ends carry out the chain extension modification, obtain hydroxy-end capped organic-silicon-modified carboxylic polyurethane oligomer or PAUR performed polymer.The isocyanate terminated based prepolymers of BAYTEC ME-230, ME-050 by MDI and PTMG preparation is abroad arranged; Prepared isocyanate terminated based prepolymers with MDI and PTMG; Synthesized polyurethane elastomer with NDI, PTMG etc.; The polyurethane liquid prepolymer that makes by reactions such as liquid terminal hydroxy group butadiene-acrylonitrile (HTBN) multipolymer and polyisocyanates; Prepared isocyanate terminated base polyurethane prepolymer for use as etc. with TDI and HTPB.Now external high-performance polyurethane elastomer mainly contains: the polyethers Acclaim type elastomerics series product of the high molecule mass of U.S. Arco company, the Desmocoll (Polyurethane Thermoplastic Elastomer) of Bayer company, the TPU (its trade(brand)name Estalo) of U.S. Goodrich company exploitation, DMC polyethers, PPDI (PPDI) type elastomerics, 1,5 naphthalene diisocyanate (NDI) type elastomerics, HTPB type elastomerics and the fluorine carbon polyurethane elastomer etc. of General Tire Inc company.With PTMG PTMEG performed polymer and diolefine type polyurethane is best, and existing commercial prod, is widely used in products such as preparation elastomerics, tackiness agent, coating, is applied to fields such as aerospace.
Conventional polyurethanes elastomeric polyethers type, polyester type etc. on the present market of China, the kind that the raw materials used polyether glycol of polyether-type performed polymer is commonly used has PPG, polytetrahydrofuran PTMEG, polycaprolactone polyol PCL etc.The supply producer of PPG is a lot, and its quality and external product have not had very difference, and the supply abundance is widely used in the conventional part substitute of rubber.PTMEG almost completely adopts imported product, quality also with Du Pont and BASF for well.The domestic manufacturer of polycaprolactone polyol is less, and quality can't guarantee, so domestic also fully by import.The shortcoming of PAUR is that hydrolytic resistance is poor, the viscosity height, rigidity is strong, the solid loading level is little; The shortcoming of polyether(poly)urethane is a poor heat resistance, and product is mainly used in automobile, building, mine and footwear and the aspect such as uses.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of quality product height, the method for preparing high performance urethane elastomer for thermal barrier coating of good combination property.
The present invention prepares the method for heat insulating coat with high-performance polyurethane elastomer, comprises following processing step:
1. the preparation of performed polymer: is that the ratio of 1:0.15～1:0.45 adds in the reactor with terminal hydroxy polybutadiene liquid rubber and polyisocyanates with the mol ratio of OH (hydroxyl) and NCO (isocyanic ester), in 80～85 ℃ of reactions 15～30 minutes down; The urethane that adds terminal hydroxy polybutadiene liquid rubber weight 1～5% again strengthens agent, continues to react 3～4 hours in 85～90 ℃, makes isocyanate terminated basic performed polymer, cooling discharge; Add the heat insulating function filler of terminal hydroxy polybutadiene liquid rubber weight 80～95%, mixing gets compound performed polymer;
2. the preparation of solidifying agent: with chainextender, anti-aging agent, solidifying agent, solvent weight ratio mixing with 1:0.5:6:16～1:0.8:8:18, composite curing agent;
3. the preparation of polyurethane elastomer: the compound performed polymer of above-mentioned preparation is mixed with the weight ratio of 3:1～6:1 with composite curing agent, stir, at room temperature solidify 60～100 hours promptly.
The number-average molecular weight of described terminal hydroxy polybutadiene liquid rubber is 3000～3500, and molecular weight distributing index is 1.4～1.7, viscosity (Pa.s, 40 ℃)＜5.0, and average functionality 2～2.3, hydroxyl value is at 0.60～0.75mmol/g, moisture＜300ppm.
Described polyisocyanates is tolylene diisocyanate or 4,4 ,-diphenylmethanediisocyanate.
It is N that described urethane strengthens agent, the derivative of two (2-hydroxypropyl) aniline of N, and its molecular structural formula is:
Its number-average molecular weight is 265～280, viscosity (Pa.s, 40 ℃)＜2.0, and hydroxyl value (mmol/g) 7.5 ± 0.1, the pH value is 7-8, moisture＜400ppm.
Described heat insulating function filler is the mixture of weight ratios such as hollow glass bead, anatase thpe white powder and light calcium carbonate.
The 2. described chainextender of step is 1,4 butyleneglycol; Solidifying agent is 3,3 ,-two chloro-4,4 ,-diamino-ditan; Anti-aging agent is a 2,6 ditertiary butyl p cresol; Solvent is the mixture of pimelinketone and tetrahydrofuran (THF), and wherein the weight percent of pimelinketone is 40～60%, and the weight percent of tetrahydrofuran (THF) is 60～40%.
The heat insulating coat high-performance polyurethane elastomer of the present invention's preparation, tensile strength: 3.50～5.80MPa, elongation at break＞220%, cohesive strength:＞10.0MPa, second-order transition temperature:＜-60 ℃, cure shrinkage:＜0.1%.
The present invention compares in prior art and has the following advantages:
1, the polyurethane elastomer of the present invention's preparation; have film forming matter high-low temperature resistant, rub resistance; good springiness, the cured article shrinking percentage is little, the body mechanical property is good, with the characteristics such as strong adhesion of ground; can be used for the protection of mechanical transmission; as the line of pipes in mine conveying belt etc., the oil production, power plant's flue etc.; also can be used as seal gum or joint sealant and be applied to industries such as electronics, space flight, weaving, good application prospects is arranged.
2, the polyurethane elastomer hydrolytic resistance of the present invention's preparation is strong, viscosity is high, rigidity is strong, the solid loading level is little; Protective coating as the flyer shell; have wear-resisting, high temperature resistant, with characteristics such as flyer base material adhesive property is good; effectively the flyer shell that passes dense atmosphere with high speed is protected; prevent that flyer from deform the flyer housing because of the compression and the fricative heat energy of ambient air, thereby influenced the performance of flyer.Use the requirement that to satisfy the protection of flyer shell fully through the user.
Embodiment
The invention will be further described below by specific embodiment.
Raw material is selected the terminal hydroxy polybutadiene liquid rubber that Lanzhou Petrochemical Company is produced for use among the embodiment: number-average molecular weight 3321, hydroxyl value be at 0.6868mmol/g, average functionality 2.3, viscosity (Pa.s, 40 ℃) 4.61.
Urethane strengthens the urethane enhancing agent II type that agent adopts Lanzhou Petrochemical Company to produce, and its molecular structural formula is:
Its number-average molecular weight is 271, viscosity (Pa.s, 40 ℃) 1.06, and hydroxyl value 7.55mmol/g, the pH value is 7.2, moisture 235ppm.
Tolylene diisocyanate, 4,4 ,-diphenylmethanediisocyanate and other raw materials obtain by buying on the market.
Embodiment 1
Preparation performed polymer: in the there-necked flask of 5 liters, add 2976 gram terminal hydroxy polybutadiene liquid rubber and be heated to 105 ± 5 ℃, vacuumize 30min (at high temperature vacuumize and further remove moisture), be cooled to 60 ℃ (prevent reacting initial temperature is too high and produce implode) then, add tolylene diisocyanate 550 grams (its OH/NCO mol ratio is 1: 0.28), be warming up between 80 ℃, isothermal reaction is after 30 minutes; Add urethane and strengthen agent II type 124 grams, be warming up to 85 ℃, isothermal reaction 4.0h vacuumizes (degassing of dewatering) 30min then, obtain isocyanate terminated base fluid body rubber performed polymer (NCO content is 5.41% in the isocyanate terminated base fluid body rubber of the gained performed polymer), cooling discharge; Add the dry heat insulating function filler of crossing 3186 grams then, mixing gets compound performed polymer (being component A).Wherein the heat insulating function filler be hollow glass bead, anatase thpe white powder and light calcium carbonate etc. the weight ratio mixture.
Preparation solidifying agent: with 1,4 butyleneglycols, 68 grams, 2,6 ditertiary butyl p cresol 40 grams, 3,3,-two chloro-4,4 ,-diamino-ditan 450 grams, be dissolved in the mixture (it is 40%, 60% that pimelinketone and tetrahydrofuran (THF) get weight percent) of 1100 gram pimelinketone and tetrahydrofuran (THF), get composite curing agent (being B component).
Make polyurethane elastomer: A component and B component were got the weight ratio mixing and stirring with 4.1: 1, solidified 90 hours under the room temperature.The high-performance polyurethane elastomer that obtains.
The product tensile strength is: 4.11MPa, and elongation at break 388%, cohesive strength: 11.7MPa, second-order transition temperature :-70 ℃, cure shrinkage: 0.08%.
Embodiment 2
Preparation performed polymer: in the there-necked flask of 5 liters, add 3136 gram terminal hydroxy polybutadiene liquid rubber and be heated to 105 ± 5 ℃, vacuumize 30min, be cooled to 60 ℃ then, add tolylene diisocyanate 566 grams (its OH/NCO mol ratio 1:0.24), be warming up to 83 ℃, isothermal reaction 30 minutes; Add urethane again and strengthen agent II type 64 grams, be warming up to 88 ℃, isothermal reaction 4.5h; Vacuumize 30min then, obtain isocyanate terminated base fluid body rubber performed polymer (in the isocyanate terminated base fluid body rubber of the gained performed polymer NCO get content be 5.08%), cooling discharge.Add the dry heat insulating function filler of crossing 3390 grams, mixing gets compound performed polymer (being component A).Wherein the heat insulating function filler be hollow glass bead, anatase thpe white powder and light calcium carbonate etc. the weight ratio mixture.
Preparation solidifying agent: with 1,4 butyleneglycols, 70 grams, 2,6 ditertiary butyl p cresol 45 grams, 3,3,-two chloro-4,4 ,-diamino-ditan 480 grams, be dissolved in the mixture (it is 50%, 50% that pimelinketone and tetrahydrofuran (THF) get weight percent) of 1200 gram pimelinketone and tetrahydrofuran (THF), get composite curing agent (being B component).
Preparation polyurethane elastomer: A component and B component are mixed with the weight ratio of 4.3:1, stir, in self-vulcanizing 85 hours, the high-performance polyurethane elastomer that obtains.
The tensile strength of product is: 5.22MPa, and elongation at break 362%, cohesive strength: 11.1MPa, second-order transition temperature :-68 ℃, cure shrinkage:＜0.05%.。
Embodiment 3
Preparation performed polymer: in the there-necked flask of 5 liters, add 3217.5 gram terminal hydroxy polybutadiene liquid rubber and be heated to 105 ± 5 ℃, vacuumize 30min, be cooled to 60 ℃ then, add 4,4,-diphenylmethanediisocyanate 585.4 grams (its OH/NCO mol ratio 1:0.31) are warming up to 83 ℃, react 20 minutes; Add urethane again and strengthen agent II type 82.5 grams, be warming up to 87 ℃, isothermal reaction 4.0h vacuumizes 40min then, obtain isocyanate terminated base fluid body rubber performed polymer (content of NCO is 5.26% in the isocyanate terminated base fluid body rubber of the gained performed polymer), cooling discharge.Add the dry heat insulating function filler of crossing 3310 grams then, mixing gets compound performed polymer (being component A).Wherein the heat insulating function filler be hollow glass bead, anatase thpe white powder and light calcium carbonate etc. the weight ratio mixture.
Preparation solidifying agent: with 1,4 butyleneglycols, 75 grams, 2,6 ditertiary butyl p cresol 53 grams, 3,3,-two chloro-4,4 ,-diamino-ditan 530 grams, be dissolved in the mixture (it is 60%, 40% that pimelinketone and tetrahydrofuran (THF) get weight percent) of 1300 gram pimelinketone and tetrahydrofuran (THF), get composite curing agent (being B component);
The preparation polyurethane elastomer: A component and B component are mixed with the weight ratio of 4.5:1, stir, in self-vulcanizing 90 hours, the high-performance polyurethane elastomer product that obtains.
The tensile strength of product is: 5.07MPa, and elongation at break 309%, cohesive strength: 10.9MPa, second-order transition temperature :-70 ℃, cure shrinkage: 0.07%.
Claims (8)
1. method for preparing high performance urethane elastomer for thermal barrier coating comprises following processing step:
1. the preparation of performed polymer: is that 1: 0.15～1: 0.45 ratio adds in the reactor with terminal hydroxy polybutadiene liquid rubber and polyisocyanates with the mol ratio of hydroxyl and isocyanate group, in 80～85 ℃ of reactions 15～30 minutes down; The urethane that adds terminal hydroxy polybutadiene liquid rubber weight 1～5% again strengthens agent, continues to react 3～4 hours in 85～90 ℃, makes isocyanate terminated basic performed polymer, cooling discharge; Add the heat insulating function filler of terminal hydroxy polybutadiene liquid rubber weight 80～95%, mixing gets compound performed polymer;
It is N that described urethane strengthens agent, the derivative of two (2-hydroxypropyl) aniline of N, and its molecular structural formula is:
Its number-average molecular weight is 271, viscosity＜2.0Pa.s, and 40 ℃, hydroxyl value 7.5 ± 0.1mmol/g, the pH value is 7～8, moisture＜400ppm;
Described heat insulating function filler is the mixture of weight ratios such as hollow glass bead, anatase thpe white powder and light calcium carbonate;
2. the preparation of solidifying agent: with chainextender, anti-aging agent, solidifying agent, solvent with 1: 0.5: 6: 16～1: 0.8: 8: 18 weight ratio mixing, composite curing agent;
3. the preparation of polyurethane elastomer: the compound performed polymer of above-mentioned preparation is mixed with 3: 1～6: 1 weight ratio with composite curing agent, stir, at room temperature solidify 60～100 hours promptly.
2. method for preparing high performance urethane elastomer for thermal barrier coating according to claim 1, it is characterized in that: the number-average molecular weight of described terminal hydroxy polybutadiene liquid rubber is 3000～3500, molecular weight distributing index is 1.4～1.7, viscosity＜5.0Pa.s, 40 ℃, average functionality 2～2.3, hydroxyl value be at 0.60～0.75mmol/g, moisture＜300ppm.
3. method for preparing high performance urethane elastomer for thermal barrier coating according to claim 1, it is characterized in that: described polyisocyanates is tolylene diisocyanate or 4,4 ,-diphenylmethanediisocyanate.
4. method for preparing high performance urethane elastomer for thermal barrier coating according to claim 1, it is characterized in that: step is 1. middle to be heated to 105 ± 5 ℃ with terminal hydroxy polybutadiene liquid rubber earlier, vacuumize and remove moisture, be cooled to 60 ± 5 ℃ then, react with polyisocyanates again.
5. method for preparing high performance urethane elastomer for thermal barrier coating according to claim 1, it is characterized in that: the 2. described chainextender of step is 1,4 butyleneglycol.
6. method for preparing high performance urethane elastomer for thermal barrier coating according to claim 1, it is characterized in that: the 2. described solidifying agent of step is 3,3 ,-two chloro-4,4 ,-diamino-ditan.
7. method for preparing high performance urethane elastomer for thermal barrier coating according to claim 1, it is characterized in that: the 2. described anti-aging agent of step is a 2,6 ditertiary butyl p cresol.
8. method for preparing high performance urethane elastomer for thermal barrier coating according to claim 1, it is characterized in that: the mixture that the 2. described solvent of step is pimelinketone and tetrahydrofuran (THF), wherein the weight percent of pimelinketone is 40～60%, and the weight percent of tetrahydrofuran (THF) is 60～40%.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101613453B (en) * | 2009-07-23 | 2012-07-04 | 中国铁道科学研究院金属及化学研究所 | Resin composition for filling unit plate type ballastless track convex baffling platform |
| CN101824157A (en) * | 2010-04-28 | 2010-09-08 | 南京大学 | Method for modifying cyanate ester resin by hydroxyl-terminated polybutadiene |
| CN102516488B (en) * | 2011-12-07 | 2013-06-12 | 华南理工大学 | Polymer type anti-oxidant, preparation method thereof, and application thereof |
| CN103382363B (en) * | 2013-07-08 | 2016-03-09 | 苏州靖羽新材料有限公司 | Snappiness frie retardant coating |
| CN103821005B (en) * | 2014-03-18 | 2015-09-02 | 金华市亚轮化纤有限公司 | A kind of solvent-free fiber impregnation composition and method of making the same |
| CN104004153A (en) * | 2014-06-13 | 2014-08-27 | 奥斯汀新材料（张家港）有限公司 | Method for manufacturing acid and alkali resistant thermoplastic polyurethane elastomer |
| CN105273158B (en) * | 2015-11-16 | 2018-03-23 | 烟台德邦科技有限公司 | A kind of synthetic method of low-shrinkage fourth hydroxyl type polyurethane |
| CN105906779A (en) * | 2016-04-19 | 2016-08-31 | 滁州环球聚氨酯科技有限公司 | High-strength flame-retardant modified polyurethane composite material |
| CN108586689B (en) * | 2017-12-29 | 2020-12-04 | 东莞市雄林新材料科技股份有限公司 | Polyurethane elastomer material for building jointed boards and preparation method thereof |
| CN112795177A (en) * | 2019-11-13 | 2021-05-14 | 天津市橡胶工业研究所有限公司 | Low-water-absorption polyurethane encapsulating material and preparation method thereof |
| CN113122124B (en) * | 2021-04-06 | 2022-04-22 | 宋成镇 | Expansion type flame-retardant heat-insulating fireproof coating and preparation method thereof |
| CN116239947A (en) * | 2022-12-09 | 2023-06-09 | 株洲飞鹿高新材料技术股份有限公司 | Single-component polyurethane coating and preparation method thereof |
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