CN104945594A - Polyurethane with characteristics of hydrolysis resistance and low temperature resistance, and preparation method thereof - Google Patents
Polyurethane with characteristics of hydrolysis resistance and low temperature resistance, and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
Abstract
The present invention provides a polyurethane with characteristics of hydrolysis resistance and low temperature resistance, wherein the polyurethane is produced mainly from a first intermediate and a second intermediate. According to the present invention, the hydrolysis resistance time of the polyurethane of the present invention is 28 days and is four times the hydrolysis resistance time of the normal hydrolysis resistance polyurethane, the physical retention rate achieves more than or equal to 80%, the low temperature resistance effect is excellent, and no crack grows after hydrolysis for 28 days and folding 100000 times at a temperature of -40 DEG C; and the polyurethane of the present invention can be used for production of various chemical industry products with high hydrolysis resistance requirements and high low-temperature-resistance requirements, wherein the products comprise shoe soles, tires and the like.
Description
Technical field
The invention belongs to chemical field, particularly relate to a kind of hydrolysis Low temperature-resistanpolyurethane polyurethane and preparation method thereof.
Background technology
Urethane is the high molecular synthetic material of a kind of performance between rubber and plastics, is characterized in that hardness setting range is wide, and the elasticity of existing rubber has again the hardness of plastics, and polyurethane elastomer has good mechanical property, wear resisting property and rebound performance.But, in some special dimension, to urethane except the wear-resisting of itself will be had, outside resilience, also need product to have splendid low temperature resistant effect and superpower anti-hydrolytic performance.
Conventional polyurethane material, the overwhelming majority is synthesized by polyester, although such product has good intensity, rebound resilience, owing to containing ester bond in product, can be hydrolyzed due to entering of moisture in use procedure, affect the life-span of product.
In addition, have improving one's methods of some routines, carry out alternative production of polyester exactly by polyether material, although such improvement solves the problem of product hydrolysis, the insufficient strength of product is good, and the not good grade of processibility can be restricted again.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of hydrolysis Low temperature-resistanpolyurethane polyurethane and preparation method thereof.
For achieving the above object and other relevant objects, the invention provides a kind of hydrolysis Low temperature-resistanpolyurethane polyurethane, form primarily of the first intermediate and the second Intermediate Preparation, wherein,
Described first intermediate is prepared from by the raw material of following parts by weight: PPG4000 (propylene oxide condenses) 50-70 part, PPG6000 20-30 part, BDO 6-10 part, glycerol 0.05-0.5 part, anti-wear agent 1.0-2.0 part, metal catalyst 0.05-0.1 part, amine catalyst 0.8-1.2 part;
Described second intermediate is prepared from by the raw material of following parts by weight: diphenylmethanediisocyanate (MDI) 50-60 part, phosphoric acid 0.001-0.005 part, PPG4000 15-30 part, PPG6000 5-10 part, propylene glycol 1-5 part, prepolymer 5-10 part, liquefied mdi (L-MDI) 2.5-3.0 part.
According to one of embodiment of the present invention, described anti-wear agent is that modification gathers propadiene, and described metal catalyst is Fomrez UL-28, and described amine catalyst is A33, and described liquefied mdi is Carbodiimide-Modified MDI.
According to another embodiment of the present invention, the preparation method of described first intermediate is: by described PPG4000, PPG6000,1,4-butyleneglycol, glycerol, anti-wear agent, metal catalyst, amine catalyst add in reactor respectively, start and stir, stir at least 2 hours in 60-65 DEG C, the acid number of testing product, hydroxyl value, moisture content, all in acceptability limit, cools to 40 DEG C, to obtain final product.
Preferably, described acid number, hydroxyl value, the acceptability limit of moisture content is: acid number≤0.3, hydroxyl value: 150-180, water ratio <0.05%.
According to the present invention's embodiment again, the preparation method of described second intermediate is: add in reactor by MDI, phosphoric acid, liquefied mdi, starts and stirs, temperature controls below 50 DEG C, add PPG4000, PPG6000, propylene glycol, 70 DEG C of reaction 0.5-1.5 hour are warmed up to after homo(io)thermism, be cooled to less than 65 DEG C, add prepolymer, be warmed up to 75 DEG C of reaction 2-4 hour, be cooled to 40 DEG C, stand-by with nitrogen encapsulation.
According to the present invention's embodiment again, the preparation method of described prepolymer is: get PPG4000 90-95 weight part and join in reactor, temperature control is in less than 50 DEG C, start and stir, slowly add diphenylmethanediisocyanate 5-10 weight part, after homo(io)thermism, be warmed up to 68-72 DEG C of isothermal reaction 2-4 hour, cool to 55 DEG C, to obtain final product.
Preferably, described prepolymer uses front nitrogen protection to preserve.
Test proves, adopt the method for secondary synthesis second intermediate, first allow a part of polyethers by the polyethers of isocyanate-modified one-tenth macromolecule, participate in the second intermediate synthesis again, the second intermediate drawn so not only has good tear strength, has higher polishing scratch and good processing effect simultaneously.
According to the present invention, described hydrolysis Low temperature-resistanpolyurethane polyurethane by the first intermediate and the second intermediate in mass ratio 100:60-70 be prepared from.
Present invention also offers the preparation method of described hydrolysis Low temperature-resistanpolyurethane polyurethane, described method mainly comprises:
(1) by described first intermediate and described second intermediate respectively at 38-42 DEG C constant temperature save backup;
(2) by mould constant temperature at 40-45 DEG C, for subsequent use;
(3) according to the density of described hydrolysis Low temperature-resistanpolyurethane polyurethane, the first intermediate is adjusted;
(4) make according to the ratio of described first intermediate and described second intermediate, prepare described hydrolysis Low temperature-resistanpolyurethane polyurethane.
Preferably, described step (3) to adjust described first intermediate by adding water.
Further preferred, amount of water is that every kilogram of described first intermediate adds water 1.5-4g.
As mentioned above, the present invention has following beneficial effect: hydrolysis Low temperature-resistanpolyurethane polyurethane hydrolysis of the present invention is 28 days, and be 4 times of common hydrolysis resistant polyurethane time, physical property conservation rate reaches more than 80%; Low temperature resistant excellent: after being hydrolyzed 28 days, rolls over 100,000 flawlesses and increases under 40 degrees below zero.Hydrolysis Low temperature-resistanpolyurethane polyurethane of the present invention can be used for producing and variously requires higher Chemicals, as sole, tire etc. to hydrolytic resistance and lower temperature resistance.
Embodiment
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Notice, in the following example, the concrete processing unit that indicates or device all adopt conventional equipment in this area or device; All force value and scope all refer to absolute pressure.
In addition should be understood that the one or more method stepss mentioned in the present invention do not repel and can also to there is additive method step or can also insert additive method step before and after described combination step between these steps clearly mentioned, except as otherwise noted; Will also be understood that, the relation that is connected between the one or more equipment/devices mentioned in the present invention is not repelled and can also to be there are other equipment/devices or can also insert other equipment/devices before and after described clustered aggregates/device between these two equipment/devices clearly mentioned, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1
First intermediate:
PPG4000 66Kg, PPG6000 24Kg, BDO 6.9Kg, glycerol 0.3Kg, modification gather propadiene 1.5Kg, Fomrez UL-28 0.08Kg (Mai Tu company product), amine catalyst A33 0..9Kg; Preparation method is: PPG4000, PPG6000, BDO, glycerol, modification are gathered propadiene, metal catalyst, amine catalyst and add respectively in reactor, starts and stirs; stir at least 3 hours in 60-63 DEG C; the acid number of testing product, hydroxyl value, moisture; to acid number≤0.3; hydroxyl value: 150-180, water ratio <0.05%, cools to 40 DEG C; logical nitrogen protection, for subsequent use.
Prepolymer:
Getting PPG4000 94Kg joins in reactor, and temperature control, in less than 50 DEG C, starts and stirs, slowly add diphenylmethanediisocyanate 6Kg, be warmed up to 70 DEG C of isothermal reactions 2.5 hours, cool to 55 DEG C after homo(io)thermism, and inflated with nitrogen is protected, for subsequent use.
Second intermediate:
Diphenylmethanediisocyanate (MDI) 55Kg, phosphoric acid 0.004Kg, PPG4000 18Kg, PPG6000 8Kg, propylene glycol 4Kg, prepolymer 6Kg, Carbodiimide-Modified MDI 2.6Kg.Preparation method is: add in reactor by MDI, phosphoric acid, Carbodiimide-Modified MDI, and start and stir, temperature controls below 50 DEG C, add PPG4000, PPG6000, propylene glycol, is warmed up to 70 DEG C of reactions 1 hour after homo(io)thermism, be cooled to less than 65 DEG C, add prepolymer, be warmed up to 75 DEG C of reactions 3 hours, be cooled to 40 DEG C, with nitrogen encapsulation, stand-by.
The preparation method of hydrolysis Low temperature-resistanpolyurethane polyurethane, mainly comprises:
(1) by the first intermediate and the second intermediate respectively at 39 DEG C constant temperature save backup;
(2) by mould constant temperature at 43 DEG C, for subsequent use;
(3) according to the density (0.65 gram/cc) of described hydrolysis Low temperature-resistanpolyurethane polyurethane, first intermediate that adds water adjusts; Every kilogram of first intermediate adds water 3.3g;
(4) first intermediates and the second intermediate are made in the ratio of 100:64, prepare described hydrolysis Low temperature-resistanpolyurethane polyurethane.
Embodiment 2
First intermediate:
PPG4000 50Kg, PPG6000 20Kg, BDO 10Kg, glycerol 0.5Kg, modification gather propadiene 1.0Kg, Fomrez UL-28 0.1Kg (Mai Tu company product), amine catalyst A33 0.8Kg; Preparation method is: PPG4000, PPG6000, BDO, glycerol, modification are gathered propadiene, metal catalyst, amine catalyst and add respectively in reactor, starts and stirs; stir 4 hours in 60 DEG C; the acid number of testing product, hydroxyl value, moisture; to acid number≤0.3; hydroxyl value: 150-180, water ratio <0.05%, cools to 40 DEG C; logical nitrogen protection, for subsequent use.
Prepolymer:
Getting PPG4000 90Kg joins in reactor, and temperature control, in less than 50 DEG C, starts and stirs, slowly add diphenylmethanediisocyanate 10Kg, be warmed up to 68 DEG C of isothermal reactions 4 hours, cool to 55 DEG C after homo(io)thermism, and inflated with nitrogen is protected, for subsequent use.
Second intermediate:
Diphenylmethanediisocyanate (MDI) 50Kg, phosphoric acid 0.001Kg, PPG4000 15Kg, PPG6000 5Kg, propylene glycol 1Kg, prepolymer 5Kg, Carbodiimide-Modified MDI 2.5Kg.Preparation method is: add in reactor by MDI, phosphoric acid, Carbodiimide-Modified MDI, and start and stir, temperature controls below 50 DEG C, add PPG4000, PPG6000, propylene glycol, is warmed up to 70 DEG C of reactions 0.5 hour after homo(io)thermism, be cooled to less than 65 DEG C, add prepolymer, be warmed up to 75 DEG C of reactions 4 hours, be cooled to 40 DEG C, with nitrogen encapsulation, stand-by.
The preparation method of hydrolysis Low temperature-resistanpolyurethane polyurethane, mainly comprises:
(1) by the first intermediate and the second intermediate respectively at 38-42 DEG C constant temperature save backup;
(2) by mould constant temperature at 40-45 DEG C, for subsequent use;
(3) according to the density (0.55 gram/cc) of hydrolysis Low temperature-resistanpolyurethane polyurethane, first intermediate that adds water adjusts; Every kilogram of described first intermediate adds water 54g;
(4) first intermediates and the second intermediate are made in the ratio of 100:605, prepare described hydrolysis Low temperature-resistanpolyurethane polyurethane.
Embodiment 3
First intermediate:
PPG4000 70Kg, PPG6000 30Kg, BDO 10Kg, glycerol 0.5Kg, modification gather propadiene 2.0Kg, Fomrez UL-28 0.1Kg (Mai Tu company product), amine catalyst A33 1.2Kg; Preparation method is: PPG4000, PPG6000, BDO, glycerol, modification are gathered propadiene, metal catalyst, amine catalyst and add respectively in reactor, starts and stirs; stir at least 2 hours in 65 DEG C; the acid number of testing product, hydroxyl value, moisture; to acid number≤0.3; hydroxyl value: 150-180, water ratio <0.05%, cools to 40 DEG C; logical nitrogen protection, for subsequent use.
Prepolymer:
Getting PPG4000 95Kg joins in reactor, and temperature control, in less than 50 DEG C, starts and stirs, slowly add diphenylmethanediisocyanate 5Kg, be warmed up to 72 DEG C of isothermal reactions 2 hours, cool to 55 DEG C after homo(io)thermism, and inflated with nitrogen is protected, for subsequent use.
Second intermediate:
Diphenylmethanediisocyanate (MDI) 60Kg, phosphoric acid 0.005Kg, PPG4000 30Kg, PPG6000 10Kg, propylene glycol 5Kg, prepolymer 10Kg, Carbodiimide-Modified MDI 3.0Kg.Preparation method is: add in reactor by MDI, phosphoric acid, Carbodiimide-Modified MDI, and start and stir, temperature controls below 50 DEG C, add PPG4000, PPG6000, propylene glycol, is warmed up to 70 DEG C of reactions 1.5 hours after homo(io)thermism, be cooled to less than 65 DEG C, add prepolymer, be warmed up to 75 DEG C of reactions 2 hours, be cooled to 40 DEG C, with nitrogen encapsulation, stand-by.
The preparation method of hydrolysis Low temperature-resistanpolyurethane polyurethane, mainly comprises:
(1) by the first intermediate and the second intermediate respectively at 38-42 DEG C constant temperature save backup;
(2) by mould constant temperature at 40-45 DEG C, for subsequent use;
(3) according to the density (0.85 gram/cc) of described hydrolysis Low temperature-resistanpolyurethane polyurethane, first intermediate that adds water adjusts; Every kilogram of described first intermediate adds water 1.5g;
(4) first intermediates and the second intermediate are made in the ratio of 100:70, prepare described hydrolysis Low temperature-resistanpolyurethane polyurethane.
Embodiment 4
First intermediate:
PPG4000 60Kg, PPG6000 25Kg, BDO 8Kg, glycerol 0.35Kg, modification gather propadiene 1.6Kg, Fomrez UL-28 0.09Kg (Mai Tu company product), amine catalyst A33 0.82Kg; Preparation method is: PPG4000, PPG6000, BDO, glycerol, modification are gathered propadiene, metal catalyst, amine catalyst and add respectively in reactor, starts and stirs; stir at least 2 hours in 62-63 DEG C; the acid number of testing product, hydroxyl value, moisture; to acid number≤0.3; hydroxyl value: 150-180, water ratio <0.05%, cools to 40 DEG C; logical nitrogen protection, for subsequent use.
Prepolymer:
Getting PPG4000 94Kg joins in reactor, and temperature control, in less than 50 DEG C, starts and stirs, slowly add diphenylmethanediisocyanate 6Kg, be warmed up to 71 DEG C of isothermal reactions 3 hours, cool to 55 DEG C after homo(io)thermism, and inflated with nitrogen is protected, for subsequent use.
Second intermediate:
Diphenylmethanediisocyanate (MDI) 55Kg, phosphoric acid 0.004Kg, PPG4000 23Kg, PPG6000 6Kg, propylene glycol 3.3Kg, prepolymer 6Kg, Carbodiimide-Modified MDI 2.8Kg.Preparation method is: add in reactor by MDI, phosphoric acid, Carbodiimide-Modified MDI, and start and stir, temperature controls below 50 DEG C, add PPG4000, PPG6000, propylene glycol, is warmed up to 70 DEG C of reactions 1.4 hours after homo(io)thermism, be cooled to less than 65 DEG C, add prepolymer, be warmed up to 75 DEG C of reactions 3 hours, be cooled to 40 DEG C, with nitrogen encapsulation, stand-by.
The preparation method of hydrolysis Low temperature-resistanpolyurethane polyurethane, mainly comprises:
(1) by the first intermediate and the second intermediate respectively at 38-42 DEG C constant temperature save backup;
(2) by mould constant temperature at 40-45 DEG C, for subsequent use;
(3) according to the density (0.75 gram/cc) of described hydrolysis Low temperature-resistanpolyurethane polyurethane, first intermediate that adds water adjusts; Every kilogram of described first intermediate adds water 2.5g;
(4) first intermediates and the second intermediate are made in the ratio of 100:68, prepare described hydrolysis Low temperature-resistanpolyurethane polyurethane.
Test example
1. in order to better evaluate the performance of product of the present invention, we set the density of goods according to GB testing requirement, make test piece test with the test piece mould of 200MM (length) * 100MM (wide) * 6MM (thick).
2. used normal polyester material respectively in test, the polyurethane material in common polyether material and embodiment 1 is made in same density, after 100 DEG C * 24, carry out physical property measurement contrast to it.(test performance sees the following form)
Can draw from above test result:
1. polyester test piece, tensile strength at normal temperatures, elongation, tear strength is all higher, but product is not low temperature resistant, not hydrolysis, cannot reach the requirement of client.
2. conventional polyether test piece, although low temperature resistant, hydrolysis effect is passable, the tensile strength under normal temperature, elongation, and tear strength is all not high, cannot meet customer requirement yet.
3. the hydrolysis Low temperature-resistanpolyurethane polyurethane of the present invention test piece of getting, has following characteristics:
A. low temperature resistant effect is better, and 40 degrees below zero is rolled over 100,000 flawlesses and increased;
B. wear resistance is good, and in the polyethers formula of same anti-wear agent, polishing scratch is obviously much lower;
C. the stretching under normal temperature, elongation and tear strength reach the physical property of polyester substantially;
D. low temperature resistant, hydrolysis ultra-long time also has good physical property after (28 days).
Above embodiment is in order to embodiment disclosed by the invention is described, can not be interpreted as limitation of the present invention.In addition, various amendment listed herein and invention in method, composition change, be apparent concerning those skilled in the art without departing from the scope and spirit in the present invention.Although in conjunction with multiple concrete preferred embodiment of the present invention to invention has been concrete description, should be appreciated that the present invention should not be only limitted to these specific embodiments.In fact, variously as above invention is obtained concerning apparent amendment those skilled in the art and all should comprise within the scope of the invention.
Claims (9)
1. a hydrolysis Low temperature-resistanpolyurethane polyurethane, forms primarily of the first intermediate and the second Intermediate Preparation, wherein,
Described first intermediate is prepared from by the raw material of following parts by weight: PPG4000 (propylene oxide condenses) 50-70 part, PPG600020-30 part, BDO 6-10 part, glycerol 0.05-0.5 part, anti-wear agent 1.0-2.0 part, metal catalyst 0.05-0.1 part, amine catalyst 0.8-1.2 part;
Described second intermediate is prepared from by the raw material of following parts by weight: diphenylmethanediisocyanate (MDI) 50-60 part, phosphoric acid 0.001-0.005 part, PPG400015-30 part, PPG60005-10 part, propylene glycol 1-5 part, prepolymer 5-10 part, liquefied mdi (L-MDI) 2.5-3.0 part.
2. hydrolysis Low temperature-resistanpolyurethane polyurethane as claimed in claim 1, it is characterized in that, described anti-wear agent is that modification gathers propadiene, and described metal catalyst is Fomrez UL-28, and described amine catalyst is A33, and described liquefied mdi is Carbodiimide-Modified MDI.
3. hydrolysis Low temperature-resistanpolyurethane polyurethane as claimed in claim 1, it is characterized in that, the preparation method of described first intermediate is: described PPG4000, PPG6000, BDO, glycerol, anti-wear agent, metal catalyst, amine catalyst are added respectively in reactor, starts and stirs, stir at least 2 hours in 60-65 DEG C, the acid number of testing product, hydroxyl value, moisture content is all in acceptability limit, cool to 40 DEG C, to obtain final product; Wherein, described acid number, hydroxyl value, the acceptability limit of moisture content is: acid number≤0.3, hydroxyl value: 150-180, water ratio <0.05%.
4. hydrolysis Low temperature-resistanpolyurethane polyurethane as claimed in claim 1, it is characterized in that, the preparation method of described second intermediate is: add in reactor by MDI, phosphoric acid, liquefied mdi, start and stir, temperature controls, below 50 DEG C, to add PPG4000, PPG6000, propylene glycol, is warmed up to 70 DEG C of reaction 0.5-1.5 hour, is cooled to less than 65 DEG C after homo(io)thermism, add prepolymer, be warmed up to 75 DEG C of reaction 2-4 hour, be cooled to 40 DEG C, stand-by with nitrogen encapsulation.
5. hydrolysis Low temperature-resistanpolyurethane polyurethane as described in claim 1 or 5, it is characterized in that, the preparation method of described prepolymer is: get PPG400090-95 weight part and join in reactor, temperature control is in less than 50 DEG C, start and stir, slowly add diphenylmethanediisocyanate 5-10 weight part, after homo(io)thermism, be warmed up to 68-72 DEG C of isothermal reaction 2-4 hour, cool to 55 DEG C, to obtain final product.
6. hydrolysis Low temperature-resistanpolyurethane polyurethane as described in any one of claim 1-5, is characterized in that, described hydrolysis Low temperature-resistanpolyurethane polyurethane by the first intermediate and the second intermediate in mass ratio 100:60-70 be prepared from.
7. the preparation method of hydrolysis Low temperature-resistanpolyurethane polyurethane as claimed in claim 6, it is characterized in that, described method mainly comprises:
(1) by described first intermediate and described second intermediate respectively at 38-42 DEG C constant temperature save backup;
(2) by mould constant temperature at 40-45 DEG C, for subsequent use;
(3) according to the density of described hydrolysis Low temperature-resistanpolyurethane polyurethane, the first intermediate is adjusted;
(4) make according to the ratio of described first intermediate and described second intermediate, prepare described hydrolysis Low temperature-resistanpolyurethane polyurethane.
8. the preparation method of hydrolysis Low temperature-resistanpolyurethane polyurethane as claimed in claim 7, is characterized in that, described step (3) to adjust described first intermediate by adding water.
9. the preparation method of hydrolysis Low temperature-resistanpolyurethane polyurethane as claimed in claim 8, is characterized in that, amount of water is that every kilogram of described first intermediate adds water 1.5-4g.
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| CN103265685A (en) * | 2013-05-28 | 2013-08-28 | 江苏华大新材料有限公司 | Microporous polyether urethane elastomer composite material and preparation method thereof |
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