CN1068889C - Prepn. process of polyurethane-based friction disk - Google Patents
Prepn. process of polyurethane-based friction disk Download PDFInfo
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- CN1068889C CN1068889C CN97118145A CN97118145A CN1068889C CN 1068889 C CN1068889 C CN 1068889C CN 97118145 A CN97118145 A CN 97118145A CN 97118145 A CN97118145 A CN 97118145A CN 1068889 C CN1068889 C CN 1068889C
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Abstract
The present invention relates to a preparation method for polyurethane-base friction disks. The method comprises the following steps: adding a catalyst in ordinary raw polyurethane MDI as a base to carry out tripolymerization, and then making the raw polyurethane MDI react with dewatered binary alcohol to obtain a prepolymer which has a high content of rigid sections and contains heat resistant materials; adding heat resistant inorganic fillers in the prepolymer, mixing the heat resistant inorganic fillers with the prepolymer, and then adding a mixed chain extender in the obtained mixture to carrying out reaction; finally, obtaining a product via pouring, mold closing, pressurization and sulfidation. The present invention has the advantages of low cost of a product and simple and easy preparation processes, and raw expensive NDI can be replaced by raw ordinary MDI.
Description
The invention belongs to a kind of preparation method of friction disc, specifically a kind of preparation method of polyurethane-based friction disk.
Folded dish friction-type false-twisting device is one of main mode of fiber-synthesizing filament recoverable deformation processing, compare with the rotor-type scroll tube, process velocity height (900～1000m/min, rotor-type only is 150～200m/min), and easily operation, noise is low, maintenance cost is low, thereby adopts the friction-type processing mode to replace rotor-type to have become trend of the times.
Folded disc type scroll tube is that the friction disc by different quantities is installed on the driving stem of three same speed with certain spacing, alternately overlapping, processed strand with spirrillum route process, obtains twisting, backtwisting, just false twisting by direct and friction disc friction in the middle of three garden dishes.Except that shape, size, sequence, spacing and the shaft core position of friction disc, the material of garden dish has very big influence to the processing quality of silk.Friction disc commonly used has soft elastomerics (urethanes) and hard stiffener (alumina-ceramic, titanium metal pottery, duralumin etc.).By contrast, PU friction disc more is applicable to the production of fine denier filament, and it is little to have a frictional coefficient, can overcome skidding, not damage advantages such as silk ribbon, can be under lower rotating speed, obtain higher-strength, degree of stretching and good crimp property, twist homogeneity simultaneously and stablize.But, for soft elastomerics, except that requiring higher elasticity, hardness, given prominence to requirement wear-resisting, that hang down tension set and anti-Nei Shengre especially.It is serious that common polyurethane elastomer material in use softens, is out of shape, tears phenomenon, can't satisfy service requirements.At present, offshore company adopts with 1, and 5-naphthalene diisocyanate (NDI) is the polyurethane elastomer material of base.Mainly be because 1,5-naphthalene diisocyanate (NDI) raw material mix symmetry, fusing point are higher, with it is the elastomerics of raw material and diphenylmethanediisocyanate commonly used (MDI), tolylene diisocyanate (TDI) material compared, has lower damping value, the dynamic property such as wear-resisting that Nei Shengre is little and excellent, but have the higher shortcoming of price.At present, be base with common urethane raw diphenylmethanediisocyanate (MDI), by the method for rational technology modification, do not find as yet by retrieval as the friction disc material.
The purpose of this invention is to provide a kind of is base with conventional polyurethanes raw material diphenylmethanediisocyanate (MDI), and the low friction disc preparation method of price.
In numerous polymkeric substance heatproof method of modifying, we have mainly adopted following technology to improve the resistance toheat of conventional polyurethanes material, to satisfy the service requirements of friction disc.
Preparation method of the present invention is as follows:
(1) diphenylmethanediisocyanate (MDI) is added in the reactor, under whipped state, be warming up to 50～80 ℃, add 0.1～0.5% (weight ratio) catalyzer then and carry out trimerization reaction, keep reaction 10～30 minutes, add the terminator with weight such as catalyzer, promptly obtain the modification degree and be 8～25% diphenylmethanediisocyanate (MDI) solution;
(2) with diphenylmethanediisocyanate (MDI) solution of modification and the dibasic alcohol that dewaters, consist of (equivalence ratio)-NCO: OH=3 by content in the material: 1～5: 1 proportioning adds in the reactor, under whipped state, be warming up to 80～90 ℃, keep reaction 2～4 hours, make performed polymer;
(3) consist of (weight ratio) performed polymer in material: the ratio of heat-resisting mineral filler=100: 3～100: 8 adds mineral filler, obtains raw material after mixing;
(4) raw material that obtains is formed (equivalence ratio)-NCO :-OH=1 with mixed chain extender by material: mix at 0.85～1: 0.95, chain extending reaction 3～5 minutes, cast;
(5) pour mass after the pressurization, 100 ℃ of sulfurations 2～4 hours, promptly gets product through matched moulds.
Aforesaid catalyst for trimerization comprises triethylene diamine, 2,4,6-three (dimethylin) methylphenol (DMP-30), 4-methyl-2-ethyl imidazol(e) (EMI), lithium acetate.
Aforesaid terminator comprises Benzoyl chloride, methyl-sulfate, to ethylmethane sulfonate.
Aforesaid modification degree=(after the 33.6-modification-NCO%) ÷ 33.6 * 100%
In the formula: 33.6 be pure diphenylmethanediisocyanate (MDI)-NCO% content
Aforesaid dibasic alcohol comprises that molecular weight is all polyester diol such as 800～2000 poly-epsilon-caprolactone, polyethylene glycol adipate, poly-hexanodioic acid second/propylene glycol ester.
Aforesaid mineral filler comprises superfine silicon dioxide gel, wear-resisting white carbon black etc.
Aforesaid chainextender is resistance toheat Resorcinol two (beta-hydroxyethyl) ether (HQEE) preferably: dibasic alcohol: trivalent alcohol=3: 1: 1～6: 4: 1
The dibasic alcohol chainextender comprises ethylene glycol, propylene glycol, 1,4-butyleneglycol (BDO), hexylene glycol etc.
The trivalent alcohol chainextender comprises TriMethylolPropane(TMP) (TMP), glycerine, 1,2,6-hexanetriol etc.
The present invention has following advantage:
With common diphenylmethanediisocyanate (MDI) raw material replace price higher 1,5-naphthalene diisocyanate (NDI) raw material.
2. the cost of product reduces.
3. preparation process is simple, easy to operate.
4. products obtained therefrom is used for the friction disc material and has higher thermostability and excellent abrasive.
Embodiment of the present utility model is as follows:
Embodiment one
(1) takes by weighing the refining diphenylmethanediisocyanate (MDI) of 50g, add and be furnished with agitator, in the reactor of thermometer, heat temperature raising to 80 ℃ drips DMP-30 catalyzer 0.06g (0.12%), keeps 80 ℃ of temperature of reaction, drip 0.06g Benzoyl chloride terminator after 10 minutes, stir, make isocyanurate-modified diphenylmethanediisocyanate (MDI) solution, by analysis-NCO%=30.3%.The modification degree is: (33.6-30.3) ÷ 33.6 * 100%=9.82%;
(2) equivalence ratio by reactant is-NCO :-OH=3: 1 polyethylene glycol adipate dibasic alcohol (Mn=1000) 60.1g that takes by weighing dehydration progressively adds in modified diphenylmethane diisocyanate (MDI) solution, heat temperature raising to 85 ℃, keep reaction 3.0 hours, make performed polymer.Performed polymer is through deaeration post analysis :-NCO%=8.8%;
(3) by performed polymer: white carbon black=100: 3 (weight ratio) adds white carbon black in performed polymer, obtain raw material after mixing;
(4) press in the raw material-NCO: in the chainextender-OH=1: 0.95 (equivalence ratio), the raw material of getting the 50g gained mixes at 80 ℃ with the 5.74gHQEE+0.87gBDO+0.87TMP mixed chain extender, stirred 3 minutes rapidly, cast, the mixed chain extender equivalence ratio is HQEE: BDO: TMP=3: 1: 1;
(5) pour mass matched moulds after the pressurization, through 100 ℃ of sulfurations 2 hours, promptly gets product.
Embodiment two
(1) takes by weighing the refining diphenylmethanediisocyanate (MDI) of 60g, add in the reactor, heat temperature raising to 50 ℃, drip DMP-30 catalyzer 0.06g (0.1%), keep temperature of reaction, drip 0.06g methyl-sulfate terminator after 30 minutes, stir, make isocyanurate-modified diphenylmethanediisocyanate (MDI) solution, analysis-NCO%=28.5%.The modification degree is: (33.6-28.5) ÷ 33.6 * 100%=15.18%;
(2) equivalence ratio by reactant is-NCO :-OH=4: 1 poly-hexanodioic acid second/propylene glycol ester dibasic alcohol (Mn=2000) 102g that takes by weighing dehydration progressively adds in modified diphenylmethane diisocyanate (MDI) solution that makes, heat temperature raising to 83 ℃, keep reaction 3.5 hours, make performed polymer, performed polymer is through deaeration post analysis :-NCO%=7.90%;
(3) press performed polymer: superfine silicon dioxide=100: 8 (weight ratio) adds the 13g superfine silicon dioxide in performed polymer, obtain raw material after mixing;
(4) press in the gained raw material-NCO: in the chainextender-OH=1: 0.92 (equivalence ratio), the raw material of getting the 50g gained mixes at 80 ℃ with 4.51gHQEE+0.71g ethylene glycol+0.5gTMP mixed chain extender, stirred 4.5 minutes rapidly, cast, the mixed chain extender equivalence ratio is HQEE: ethylene glycol: TMP=4: 2: 1;
(5) pour mass matched moulds after the pressurization, through 100 ℃ of sulfurations 2 hours, promptly gets product.
Embodiment three
(1) takes by weighing the refining diphenylmethanediisocyanate (MDI) of 60g, add in the reactor, heat temperature raising to 65 ℃, drip triethylene diamine catalyzer 0.123g (0.205%), keep temperature of reaction, drip 0.125g after about 15 minutes, stir the ethylmethane sulfonate terminator, make isocyanurate-modified diphenylmethanediisocyanate (MDI) solution, by analysis-NCO%=27.6%.The modification degree is: (33.6-27.6) ÷ 33.6 * 100%=17.86%;
(2) equivalence ratio by reactant is-NCO :-OH=3.6: 1 poly-epsilon-caprolactone dibasic alcohol (Mn=1280) 70.1g that takes by weighing dehydration progressively adds in modified diphenylmethane diisocyanate (MDI) solution that makes, heat temperature raising to 86 ℃, keep reaction 2.5 hours, make performed polymer, performed polymer is through deaeration post analysis :-NCO%=8.9%;
(3) press performed polymer: white carbon black=100: 5 (weight ratio) adds the 6.5g white carbon black in performed polymer, obtain raw material after mixing;
(4) press in the gained raw material-NCO: in the chainextender-OH=1: 0.9 (equivalence ratio), the raw material of getting the 50g gained mixes at 80 ℃ with 5.39gHQEE+1.22gBDO+0.28g glycerine mixed chain extender, stirs cast rapidly 3.5 minutes.The mixed chain extender equivalence ratio is: HQEE: BDO: glycerine=6: 3: 1;
(5) pour mass matched moulds after the pressurization, through 100 ℃ of sulfurations 2 hours, promptly gets product.
Embodiment four
(1) takes by weighing the refining diphenylmethanediisocyanate (MDI) of 80g, add in the reactor, heat temperature raising to 60 ℃, drip EMI catalyzer 0.25g (0.313%), keep temperature of reaction, drip Benzoyl chloride terminator 0.24g after 25 minutes, stir, make isocyanurate-modified diphenylmethanediisocyanate (MDI) solution, by analysis-NCO%=26.2%.The modification degree is: (33.6-26.2) ÷ 33.6 * 100%=22.02%;
(2) equivalence ratio by reactant is-NCO :-OH=4.5: 1 takes by weighing poly-epsilon-caprolactone dibasic alcohol (Mn=1710) 94.8g of dehydration, progressively add in modified diphenylmethane diisocyanate (MDI) solution that makes, heat temperature raising to 87 ℃, keep reaction 2.5 hours, make performed polymer, performed polymer is through deaeration post analysis :-NCO%=8.6%;
(3) press performed polymer: superfine silicon dioxide=100: 6 (weight ratio) adds the 10.5g superfine silicon dioxide in performed polymer, obtain raw material after mixing;
(4) press in the gained raw material-NCO: in the chainextender-OH=1: 0.88 (equivalence ratio), the raw material of getting the 50g gained mixes at 80 ℃ with the 5.25gHQEE+0.95gBDO+0.48gTMP mixed chain extender, stirred 4 minutes rapidly, cast, the mixed chain extender equivalence ratio is: HQEE: BDO: TMP=5: 2: 1;
(5) pour mass matched moulds after the pressurization, through 100 ℃ of sulfurations 2 hours, promptly gets product.
Embodiment five
(1) takes by weighing the refining diphenylmethanediisocyanate (MDI) of 60g, add in the reactor, heat temperature raising to 70 ℃, drip DMP-30, catalyzer 0.06g (0.1%) keeps temperature of reaction, drip Benzoyl chloride terminator 0.06g after 10 minutes, stir, make isocyanurate-modified diphenylmethanediisocyanate (MDI) solution, by analysis-NCO%=30.7%.The modification degree is: (33.6-30.7) ÷ 33.6 * 100%=8.63%;
(2) equivalence ratio by reactant is-NCO :-OH=3.1: 1 takes by weighing poly-epsilon-caprolactone dibasic alcohol (Mn=1280) 90.5g of dehydration, progressively add in modified diphenylmethane diisocyanate (MDI) solution that makes, heat temperature raising to 85 ℃, keep reaction 3.0 hours, make performed polymer, performed polymer is through deaeration post analysis :-NCO%=7.6%;
(3) press performed polymer: superfine silicon dioxide=100: 5 (weight ratio) adds the 7.5g superfine silicon dioxide in performed polymer, obtain raw material after mixing;
(4) press in the gained raw material-NCO: in the chainextender-OH=1: 0.95 (equivalence ratio), the raw material of getting the 50g gained mixes at 80 ℃ with the 3.60gHQEE+1.63gBDO+0.41gTMP mixed chain extender, stirred 3 minutes rapidly, cast, the mixed chain extender equivalence ratio is: HQEE: BDO: TMP=4: 4: 1;
(5) pour mass matched moulds after the pressurization, through 100 ℃ of sulfurations 2 hours, promptly gets product.
Embodiment six
(1) takes by weighing the refining diphenylmethanediisocyanate (MDI) of 50g, add in the reactor, heat temperature raising to 50 ℃, drip triethylene diamine catalyzer 0.24g (0.48%), keep temperature of reaction, drip Benzoyl chloride terminator 0.25g after 15 minutes, stir, make isocyanurate-modified diphenylmethanediisocyanate (MDI) solution, by analysis-NCO%=26.9%.The modification degree is: (33.6-26.9) ÷ 33.6 * 100%=19.94%;
(2) equivalence ratio by reactant is-NCO :-OH=4.2: 1 poly-epsilon-caprolactone dibasic alcohol (Mn=1710) 65.2g that takes by weighing dehydration progressively adds in modified diphenylmethane diisocyanate (MDI) solution that makes, heat temperature raising to 85 ℃, keep reaction 3.5 hours, make performed polymer, performed polymer is through deaeration post analysis :-NCO%=8.4%;
(3) press performed polymer: superfine silicon dioxide=100: 5 (weight ratio) adds the 5.7g superfine silicon dioxide in performed polymer, obtain raw material after mixing;
(4) press in the gained raw material-NCO: in the chainextender-OH=1: 0.95 (equivalence ratio), the raw material of getting the 50g gained mixes at 80 ℃ with 4.97gHQEE+1.14g propylene glycol+0.45g hexanetriol mixed chain extender, stirred 3.5 minutes rapidly, cast, the mixed chain extender equivalence ratio is: HQEE: propylene glycol: hexanetriol=5: 3: 1;
(5) pour mass matched moulds after the pressurization, through 100 ℃ of sulfurations 2 hours, promptly gets product.
Claims (8)
1. the preparation method of a polyurethane-based friction disk is characterized in that:
(1) diphenylmethanediisocyanate (MDI) is added in the reactor, under whipped state, be warming up to 50-80 ℃, add 0.1～0.5% (weight ratio) catalyzer then and carry out trimerization reaction, keep reaction 10～30 minutes, add the terminator with weight such as catalyzer, promptly obtain the modification degree and be 8～25% diphenylmethanediisocyanate (MDI) solution;
(2) with diphenylmethanediisocyanate (MDI) solution of modification and the dibasic alcohol that dewaters, consist of (equivalence ratio)-NCO: OH=3 by content in the material: 1～5: 1 proportioning adds in the reactor, under whipped state, be warming up to 80～90 ℃, keep reaction 2～4 hours, make performed polymer;
(3) consist of (weight ratio) performed polymer by material: heat-resisting mineral filler=100: 3～add mineral filler at 100: 8 obtains raw material after mixing;
(4) raw material that obtains is formed (equivalence ratio)-NCO :-OH=1 with mixed chain extender by material: mix at 0.85～1: 0.95, chain extending reaction 3～5 minutes, cast;
(5) pour mass after the pressurization, 100 ℃ of sulfurations 2～4 hours, promptly gets product through matched moulds.
2. the preparation method of polyurethane-based friction disk according to claim 1, it is characterized in that described catalyst for trimerization comprises triethylene diamine, 2,4,6-three (dimethylin) methylphenol (DMP-30), 4-methyl-2-ethyl imidazol(e) (EMI), lithium acetate.
3. the preparation method of polyurethane-based friction disk according to claim 1, it is characterized in that described terminator comprise Benzoyl chloride, methyl-sulfate, to ethylmethane sulfonate.
4. the preparation method of polyurethane-based friction disk according to claim 1 is characterized in that described dibasic alcohol comprises that molecular weight is all polyester diol of 800～2000 poly-epsilon-caprolactone, polyethylene glycol adipate, poly-hexanodioic acid second, propylene glycol ester.
5. the preparation method of polyurethane-based friction disk according to claim 1 is characterized in that described mineral filler comprises superfine silicon dioxide aerogel, wear-resisting white carbon black.
6. the preparation method of polyurethane-based friction disk according to claim 1 is characterized in that described chainextender is resistance toheat Resorcinol two (beta-hydroxyethyl) ether (HQEE) preferably: dibasic alcohol: trivalent alcohol=3: 1: 1～6: 4: 1.
7. the preparation method of polyurethane-based friction disk according to claim 6 is characterized in that described dibasic alcohol chainextender comprises ethylene glycol, propylene glycol, 1,4-butyleneglycol (BDO), hexylene glycol.
8. the preparation method of polyurethane-based friction disk according to claim 6 is characterized in that described trivalent alcohol chainextender comprises TriMethylolPropane(TMP) (TMP), glycerine, 1,2,6-hexanetriol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118145A CN1068889C (en) | 1997-10-06 | 1997-10-06 | Prepn. process of polyurethane-based friction disk |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118145A CN1068889C (en) | 1997-10-06 | 1997-10-06 | Prepn. process of polyurethane-based friction disk |
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| Publication Number | Publication Date |
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| CN1213674A CN1213674A (en) | 1999-04-14 |
| CN1068889C true CN1068889C (en) | 2001-07-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97118145A Expired - Fee Related CN1068889C (en) | 1997-10-06 | 1997-10-06 | Prepn. process of polyurethane-based friction disk |
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| CN104448778B (en) * | 2014-11-27 | 2017-06-06 | 深圳市百事达卓越科技股份有限公司 | A kind of thermoplastic elastomer (TPE), the preparation method and application of conductive or static conductive |
| CN114957965A (en) * | 2022-07-07 | 2022-08-30 | 福建长泰万泰矿物制品有限公司 | High-heat-resistance polyurethane composition, polyurethane disc and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047093A (en) * | 1990-06-13 | 1990-11-21 | 机械电子工业部济南第五三研究所 | Polyurethane foam polishing sheet for polishing and method for producing same |
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1997
- 1997-10-06 CN CN97118145A patent/CN1068889C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047093A (en) * | 1990-06-13 | 1990-11-21 | 机械电子工业部济南第五三研究所 | Polyurethane foam polishing sheet for polishing and method for producing same |
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| CN1213674A (en) | 1999-04-14 |
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