WO2013091271A1

WO2013091271A1 - Microporous polyurethane elastomer composition with excellent dynamic performance and method for preparing same

Info

Publication number: WO2013091271A1
Application number: PCT/CN2012/000341
Authority: WO
Inventors: 李健; 孙清峰; 孙兆任
Original assignee: 山东东大一诺威聚氨酯有限公司
Priority date: 2011-12-23
Filing date: 2012-03-19
Publication date: 2013-06-27
Also published as: BR112013026700A2; CN102585162A

Abstract

The present invention relates to the preparation of a microporous polyurethane elastomer composition with excellent dynamic performance, consisting of a component A and a component of modified isocyanate. The component A comprises a polymer of polyol, a chain extender, a foaming agent, a catalyst A, a catalyst B, a foam stabiliser, and an anti-oxidant. The present invention has the following advantages: (1) the present invention is a microporous polyurethane elastomer material prepared by semi-prepolymerisation, and the two groups of fractional materials have similar viscosity and mixed mass ratio, a low mixture temperature; the materials are easy to mix, and the conditions for controlling the process are simple and easy to operate. (2) The microporous polyurethane elastomer material prepared from the composition provided by the present invention has a ratio of dynamic to static stiffness of ≤1.35, an impact resilience of ≥75%, a rate of change in size of ≤20%, without damage to appearance after 3 million fatigue tests, and can be used in the preparation of high performance products such as vibration-damping blocks for high speed railways and vibration-damping elements in vehicles.

Description

Microporous polyurethane elastomer composition excellent in dynamic performance and preparation method thereof

The invention belongs to the field of polyurethane elastomer synthesis, and in particular relates to the preparation of a microcellular polyurethane elastomer composition excellent in dynamic properties.

Background technique

The microporous polyurethane elastomer is a novel material between the elastomer and the foam material, and the cell diameter is generally 0.1 to 10 μ πι, the cells are fine and uniform, and the density is lower than the solid elastomer material. The mechanical properties are significantly higher than the common foam materials. Therefore, the microcellular polyurethane elastomer has the advantages of light weight, comfort and high strength of the elastomer material and good mechanical properties. It has good cushioning performance and excellent fatigue resistance. It is an elastic material with excellent comprehensive performance. It has broad application potential in some special fields, such as the application of high-speed rail cushions and the preparation of high-speed car shock absorbers.

As the operation speed of high-speed railways continues to increase, the vibration and noise generated by the vehicles are also increasing. In order to reduce the negative impact of speed increase, it is necessary to add an elastic pad between the cement sleepers and the rails when laying the railway tracks. Plates to reduce vibration and noise generated between rigid materials. The conventional railway cushion plate is made of rubber material. When the rubber material is subjected to alternating external force, the elastic recovery is relatively slow, and the dynamic and static stiffness ratio can reach 1.5 or more. It is difficult to meet the development requirements of high-speed railway. In practical applications, the method of partial grooving is often used to reduce the dynamic stiffness of the material, which results in the stress concentration at the root of the groove and the early destruction of the material, and the life is shortened. The microporous polyurethane elastomer can easily reduce the dynamic and static stiffness ratio of the material due to the regularity of the molecular structure and the strong molecular design. The conventional common polyether is obtained by ring-opening polymerization of propylene oxide and epoxy oxime. The molecular structure contains a large number of pendant methyl groups. Although the molecular structure is relatively regular, when subjected to alternating external forces, the molecular chain The motion is affected by the steric hindrance of the side base, and the deformation is lagging behind the change of stress. The energy loss becomes larger, and the dynamic and static stiffness ratio becomes larger. Therefore, the dynamic and static stiffness is also difficult to achieve the dynamic and static stiffness of the current high-speed railway pad. More than the requirements of 1.35.

Patent CN100506871C reports on a preparation method of NDI-based polyurethane microcellular elastomer. It is well known that polyurethane materials prepared by NDI have excellent dynamic performance, low damping property and high resilience, and are specially suitable for dynamic load and heat resistance. However, this material has a higher melting point, is complicated in the preparation of the polyurethane material, and has poor storage stability, and the prepared prepolymer has a storage stability time of only a few small crucibles. Patent CN101469054B reports a preparation method of PPDI-based polyurethane microcellular elastomer, which has better dynamic performance and better storage stability of prepolymer, but PPEI has higher melting point and complicated processing technology; CN101380442B reports a T0DI base. The preparation method of the polyurethane microporous elastomer has good processing performance, and the prepared polyurethane microporous elastomer material is excellent in heat resistance, wear resistance and dynamic fatigue property. However, the isocyanates used in the above patents are all special isocyanates, and the raw material cost is relatively high; on the other hand, The above patents all use the prepolymer method to prepare the microporous elastomer, the chain extension is carried out by using a small molecule mixture, the viscosity of the prepolymer component is large, the viscosity difference between the two components is large, the material mixing temperature is high, and the mass of the two components is high. The problem is larger than the gap, it is not easy to mix evenly, and the product quality is not easy to control stably.

Summary of the invention

The object of the present invention is to provide a microcellular polyurethane elastomer composition excellent in dynamic performance and a preparation method thereof, and the microporous elastomer material prepared according to the composition provided by the invention has excellent dynamic performance and resilience, dynamic and static stiffness ratio 1. 35, 3 million fatigue test after appearance without damage, impact resilience 75%, can be used for the preparation of high-speed rail cushions and automotive shock absorber components.

The microporous polyurethane elastomer composition excellent in dynamic performance according to the present invention comprises the following two components:

Component A: comprising a polymer polyol, a chain extender, a blowing agent, a catalyst A, a catalyst B, a foam stabilizer, and an antioxidant, wherein the other raw materials account for polymerization based on 100% by weight of the total of the polymer polyol. The percentage of the total weight of the polyol is: 5% to 12% of the chain extender, 0. 1%~0. 3%, the catalyst ΑΌ. 3~1. 0%, the catalyst B 0. 01%~ 0 6%; 6%; 2%; 0%, antioxidants 0. 3~0. 6%;

Component B: a modified isocyanate component, a mixture of a NC0 group-terminated urethane-modified isocyanate and an isocyanate prepared by reacting a polymer polyol with an isocyanate;

When used, component A and component B are mixed at a mass ratio of 100: 90 to 110. When mixed, the temperature of component A is 30 V to 45 ° C, and the temperature of component B is 40 ° C to 50 ° C.

When the composition of the present invention is used, the mass ratio of the component A to the component B is preferably 100: 93 to 100, more preferably 100: 95 to 97. When the two components are mixed, the component A temperature is preferably from 33 ° C to 37 ° C, and the component B temperature is preferably from 43 ° C to 47 ° C.

The polyether polyol or the average functionality of the polymer polyol is preferably from 1.8 to 4, preferably from 2 to 3, and the number average molecular weight is from 1000 to 8000, preferably from 2000 to 6000. 3, preferably 2 to 2. 5, a mixture of one or two of the polyester polyols having a number average molecular weight of from 1,000 to 6,000, preferably from 1,500 to 3,000, in any ratio. Wherein, the polyether polyol is preferably one or a mixture of one or more of a polypropylene oxide ether polyol, a propylene oxide-ethylene oxide copolyether polyol, and a polytetrahydrofuran ether polyol, more preferably a polytetrahydrofuran ether. Polyols; polyester polyols preferably from polycaprolactone polyols, polycarbonate polyols, polyadipate-1,4 butanediol ester polyols, polyadipates-1,6-hexanediol esters One or more of the polyols, more preferably a polycaprolactone polyol.

The chain extender is preferably selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol or 3,3-dichloro-4, 4- One or more of diphenyltoluenediamine.

The blowing agent is preferably one or more selected from the group consisting of water, formic acid, acetic acid or monofluorodichloroethane, more preferably water. The catalyst A is preferably selected from a tertiary amine catalyst, and may be selected from triethylene glycol of triethylenediamine having a solid content of 33%. Solution; Catalyst B is preferably one or more selected from the group consisting of an organotin catalyst, an organic ruthenium catalyst or an organozinc catalyst, and dibutyltin dilaurate may be used.

The foam stabilizer is preferably selected from the group consisting of a silicone surfactant, which may be selected from DC3043 (manufacturer of the US Gas Chemical), 8444 (manufacturer of Shanghai Gao Shimet Chemical) or AK7703 (manufacturer Nanjing Demei Shichuang). One or more.

The antioxidant is preferably a hindered phenolic antioxidant, and may be selected from BHT264 (2,6-di-tert-butyl-4-methylphenol), ChinoxlOlO (manufacturer is Taiwan Double Bond Chemical) or Irganoxl035 (manufacturer) One or more of Ciba Specialty Chemicals).

The isocyanate in the modified isocyanate component is preferably 4,4'-diphenylmethyl modified from 4,4'-diphenylmethane diisocyanate (pure MDI) or carbonized diimine-uretonimide.垸Diisocyanate (liquefied MDI), p-phenylene diisocyanate ^?01), 1,5-naphthalene diisocyanate (1) or 3,3 '-dimethyl-4,4'-biphenyldiisocyanate (T0DI) One or more.

2。 The modified isocyanate component is preferably from 11% to 14% by weight, more preferably from 12% to 12% by weight, more preferably from 2% to 25%, more preferably from 2 to 2, more preferably from 2 to 2.

The invention has the following advantages: (1) The invention adopts a semi-prepolymer method to prepare a microporous polyurethane elastomer material, the two components have similar viscosity, the mixing mass ratio is similar, the mixing temperature is low, and the material is easy to be uniformly mixed, the process The control conditions are simple and easy to operate. (2) The microporous polyurethane elastomer material prepared by the composition provided by the invention has a dynamic-static stiffness ratio of 1.35, impact resilience of 75%, no damage after 3 million fatigue tests, and a dimensional change rate of 20%, which can be used for high-speed rail Preparation of high performance products such as cushions and automotive shock absorbers. .

Detailed ways

The invention will be further described below in conjunction with the embodiments.

Example 1

Component A: Weigh 50 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) with average functionality = 2, number average molecular weight = 2000, 50 parts of polytetrahydrofuran ether with average functionality = 2, number average molecular weight = 1000 Polyol (PTMG1000, BASF product), 8 parts of 1,4-butanediol, 0.25g water, 0.5 parts AK-7703, 0.8 parts of triethylene glycol diethylene glycol with 33% solid content The solution, 0.03 parts of dibutyltin dilaurate, 0.33 parts of BHT264 in a mixer, stirred evenly, vacuum removed bubbles, sealed and stored.

Component B: 80 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) having an average functionality = 2, number average molecular weight = 2000, and 20 parts of a polyether polyol having an average functionality = 3 and a number average molecular weight = 6000 (份份,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 5小时,,,,,,,,,,,,,,,, Add 15 parts of liquefied MDI, stir for 0.5 hours, sample and test, -NC0 mass content of 13.0%, cool down to 50 ° C discharge, sealed and stored.

When used, the temperature of component A is maintained at 35 ° C, the temperature of component B is maintained at 45 ° C, and the two components are quickly mixed uniformly at a weight ratio of 100: 110, and poured into a mold which is pre-55 ° C, 85 After aging for 10 minutes in the drying tunnel of °C, the mold was opened to obtain a polyurethane microcellular elastomer material.

Example 2:

Component A: Weigh 80 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) with average functionality = 2, number average molecular weight = 2000, 20 parts of polyether polyol with average functionality = 3, number average molecular weight = 6000 Alcohol (EP-3600, Shandong Bluestar Dongda Chemical Co., Ltd.), 7 parts of 1,4-butanediol, 0.25g of water, 0.5 parts of AK-7703, 1.0 part of 33% solids of triethylenediamine The ethylene glycol solution, 0.03 parts of dibutyltin dilaurate, and 0.35 parts of BHT264 were mixed in a mixer, and the bubbles were removed by vacuum, and sealed and stored.

Component B: 100 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) with an average functionality = 2 and a number average molecular weight = 2000 were dehydrated at 110 ° C under vacuum (- 0.09 MPa) for 2 hours to ensure a moisture content of less than 0.05. °/. Then, cool down to 50 Ό, add 72.5 parts of pure MDI, slowly heat up to 75 Torr for 1.5 hours, add 15 parts of liquefied MDI, stir for 0.5 hours, sample and test, -NC0 mass content of 13.0%, cool down to 50 °C Material, sealed and stored.

Maintain the component A temperature at 35 when in use. The temperature of C and B components is maintained at 45 V. The two components are quickly mixed evenly at a weight ratio of 100:90. The mixture is poured into a mold that is pre-55 ° C. After curing for 10 minutes in a drying oven at 85 ° C, the mold is opened. A polyurethane microcellular elastomer material is obtained.

Example 3:

Component A: Weigh 80 parts of polytetrahydrofuran ether polyol with average functionality = 2 and number average molecular weight = 2000 (PTMG2000, BASF product), 20 parts of average functionality = 3, number average molecular weight = 6000 polyether Alcohol (EP-3600, Shandong Bluestar Dongda Chemical Co., Ltd.), 8.0 parts of 1,4-butanediol, 0.25g of water, 0.5 parts of DC3043, 1.0 part of triethylenediamine with a solid content of 33% The alcohol solution, 0.03 parts of dibutyltin dilaurate, and 0.35 parts of BHT264 were mixed in a mixer, and the bubbles were removed by vacuum, and sealed and stored.

Component B: 100 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) with an average functionality = 2 and a number average molecular weight = 2000 were dehydrated under vacuum (-0.09 MPa) at 110 Torr for 2 hours to ensure a moisture content of less than 0.05%. Then, the temperature was lowered to 5 CTC, and 28.1 parts of pure MDI and 28.1 parts of PPDI were added, and the temperature was raised to 85 ° C for 1.5 hours. The sample was tested, and the mass content of -NC0 was 12.8%, and the temperature was lowered to 50 Ό, and sealed and stored.

When using, maintain the temperature of component A at 35 ° C, maintain the temperature of component B at 45 Ό, and quickly mix the two components in a weight ratio of 100: 93, and pour it into a mold that is pre-55 ° C, 85 ° C. Molding in the ramp for 10 minutes, then open the mold, ie A polyurethane microcellular elastomer material is obtained.

Example 4:

A component: 100 parts of polycaprolactone polyol having an average functionality = 2, number average molecular weight = 2000 (CAPA2200 _: British Solvay product), 5 parts of ethylene glycol, 0. 27 g of water, 0. 5 parts DC3043, 1.0 part solid solution 33% triethylenediamine diethylene glycol solution, 0.03 parts dibutyltin dilaurate, 0.33 parts BHT264 in a mixer, stirred evenly, vacuum removal Bubbles, sealed and preserved.

05%, the moisture content is less than 0.05%, the moisture content is less than 0. 05%, the moisture content is less than 0. 05%, the moisture content is less than 0. 05%, 5小时进行质量质量13。 Then, the temperature was reduced to 50 ° C, the addition of 72.5 parts of pure MDI, slowly heated to 75 times the incubation reaction 1. 5 hours, adding 15 parts of liquefied MDI, stirring 0. 5 hours, sampling test, - NC0 mass content of 13. 1%, cooled to 50 ° C discharge, sealed and stored.

When used, the temperature of component A is maintained at 35 ° C, the temperature of component B is maintained at 45 ° C, and the two components are quickly mixed uniformly at a weight ratio of 100: 92, poured into a mold of 55 预, and baked at 85 Ό. After the mold is aged for 10 minutes, the mold is opened, and a polyurethane microporous elastomer material is obtained.

Example 5

A component: 100 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) having an average functionality = 2, number average molecular weight = 2000, 9 parts of diethylene glycol, 0.25 g of water, 0. 5 parts AK-7703, 1.0 part solid solution 33% triethylenediamine diethylene glycol solution, 0.03 part dibutyltin dilaurate, 0.33 parts BHT264 in a mixer, stir evenly, vacuum Remove the bubbles and store them in a sealed form.

Component B: 100 parts of polytetrahydrofuran ether polyol (PTMG2000, BASF product) with an average functionality = 2 and a number average molecular weight = 2000 were dehydrated under vacuum at 11 CTC (-0.09 MPa) for 2 hours to ensure a moisture content of less than 0. 0 重量,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Cool down to 50 ° C discharge, sealed and stored.

When used, the temperature of component A was maintained at 35 ° C and the temperature of component B was maintained at 45. C, the two components are quickly mixed uniformly according to the weight ratio of 100 _: 95, poured into a mold of 55 预, and the mold is opened after being aged for 10 minutes in an 85 烘 drying tunnel to obtain a polyurethane microcellular elastomer material.

The performance indexes of the polyurethane microcellular elastomer materials obtained in Examples 1 to 5 are as follows:

Claims

A microcellular polyurethane elastomer composition excellent in dynamic performance, which is characterized by being composed of the following two components: Component A: comprising a polymer polyol, a chain extender, a foaming agent, a catalyst A, a catalyst B, a foam stabilizer and an antioxidant, wherein, based on 100% by weight of the total weight of the polymer polyol, the percentage of other raw materials in the total weight of the polymer polyol is: 5% to 12% of the chain extender, foaming 2%1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 3~0. 6%;

When used, the components A and B are mixed according to a mass ratio of 100: 90 to 110, and the temperature of the component A is 30 Ό to 45 ° C when mixed, and the temperature of the component B is 40 ° C to 50 ° C.

The average functionality is 1. 8~4, preferably 2~3, and the average number of the polymer polyols. a polyether polyol having a relative molecular mass of from 1000 to 8000, preferably from 2000 to 6000, or an average functionality of from 2 to 3, preferably from 2 to 2. 5, a number average molecular weight of from 1000 to 6000, preferably from 1500 to 3,000. One or two mixtures of alcohols in any ratio.

The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 2, wherein the polyether polyol is selected from the group consisting of polyglycidyl ether polyols, epoxidizer-epoxy a mixture of one or more of a ruthenium copolyether polyol and a polytetrahydrofuran ether polyol, preferably a polytetrahydrofuran ether polyol; the polyester polyol is selected from the group consisting of polycaprolactone polyols, polycarbonate polyols, poly One or more of adipic acid-1,4-butylene glycol ester polyol, polyhexamethylenedicarboxylic acid-1,6-hexanediol polyol, preferably polycaprolactone polyol.

The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the chain extender is selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, and 1, One or more of 4-butanediol, 1,6-hexanediol or 3,3-dichloro-4,4-diphenyltoluenediamine.

The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the foaming agent is one or more selected from the group consisting of water, formic acid, acetic acid or monofluorodichloroethane. Kind of, preferably water. '

The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the catalyst A is selected from the group consisting of tertiary amine catalysts; and the catalyst B is selected from the group consisting of organotin catalysts and organic hydrazines. One or more of a catalyst or an organozinc catalyst.

The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the foam stabilizer is selected from the group consisting of silicone surfactants, preferably one or more of DC3043, 8444 or AK7703. Kind.

The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the antioxidant is selected from the group consisting of hindered phenol antioxidants, preferably BHT264, ChinoxlO10 or Ir _ga no _X 1035. One or more of them.

The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the isocyanate in the modified isocyanate component is selected from the group consisting of 4,4'-diphenylformamidine diisocyanate, Carbonized diimine-ureido ketimine modified 4,4 '-diphenylmethane diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate or 3, 3'-dimethyl-4, 4' One or more of biphenyl diisocyanate.

The microcellular polyurethane elastomer composition excellent in dynamic performance according to claim 1, wherein the modified isocyanate component has an isocyanate mass content of 11% to 14%, preferably 12% to 12%. 5%。 The average functionality is 2~3, preferably 2~2.