CN111393833A - High-opening-rate hydrolysis-resistant polyurethane foam and preparation method and application thereof - Google Patents
High-opening-rate hydrolysis-resistant polyurethane foam and preparation method and application thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- 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
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6622—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
Abstract
The invention relates to high-aperture-ratio hydrolysis-resistant polyurethane foam, a preparation method and application thereof, and mainly solves the technical problems of low aperture ratio and poor high-temperature high-humidity dimensional stability of polyurethane foam in the prior art. The high-aperture-ratio hydrolysis-resistant polyurethane foam is composed of a component A and a component B, wherein the weight part ratio of the component A to the component B is 100: 130-170, the component A comprises 35-60 parts of polyether polyol I, 30-60 parts of polyether polyol II, 5-10 parts of a chain extender, 1-3 parts of a cross-linking agent, 0.1-1 part of a reaction type catalyst, 0.1-1 part of a surfactant, 0.3-1.2 parts of a pore-forming agent and 2.5-4 parts of water, and the component B comprises 30-70 parts of isocyanate, 30-50 parts of modified isocyanate and 5-20 parts of a hydrolysis stabilizer.
Description
Technical Field
The invention relates to high-opening-rate hydrolysis-resistant polyurethane foam and a preparation method and application thereof.
Background
Polyurethane foaming technology has been widely applied to the preparation of automotive interior composite materials, wherein a large amount of polyurethane semi-rigid foam materials are adopted for the soft decorative layer in the automotive ceiling composite materials, and the polyurethane semi-rigid foam materials have been consistently and well received by the industry because of the characteristics of excellent light weight, heat insulation, sound absorption and the like. However, the aperture ratio of the mainstream products with the core density of 28-33 kg/m3 on the market is generally low, and the dimensional change rate is more than or equal to 2% after high temperature and high humidity, which can cause the problems of delamination, cracking, dimensional shrinkage and the like of the foam in the compounding process, and can seriously affect the normal production of manufacturers.
There are generally two methods for improving the cell opening properties of polyurethane foams: the physical method and the chemical method, the former mainly comprises the steps of mechanically rolling cured foam, vacuumizing and the like to improve the aperture ratio, but the method aims at the high-resilience flexible polyurethane foam and the semi-rigid polyurethane foam, because of special physical structures and purposes, the method cannot be adopted to improve the aperture performance, and the latter realizes the aperture by adjusting the formula, such as reasonably matching a catalyst and silicone oil to control the gel reaction and the foaming reaction of the system to be balanced.
Hydrolytic stability typically includes hydrolytic stability under high temperature and high humidity conditions and hydrolytic stability under conventional low temperature conditions.
The hydrolytic stability under the high-temperature and high-humidity condition refers to that the foam can still keep the size unchanged basically after being placed for 5 hours at the temperature of more than or equal to 120 ℃ and the humidity of more than or equal to 95 percent and then dried for 3 hours at 70 ℃, and after the circulation is carried out for 3 times, the size of the foam can still be kept unchanged, for semi-rigid polyurethane foam, the size change rate is larger due to the low opening rate of the semi-rigid polyurethane foam when the semi-rigid polyurethane foam is under the high-temperature and high-humidity condition, so that the size change rate can be reduced by improving the opening rate of the foam, but for high-end vehicle types, the required size change rate is less than or equal to 1 percent, a proper hydrolytic stabilizer needs to be introduced, and specific groups in the hydrolytic stabilizer can react with carboxyl generated by the.
The hydrolysis stability under the conventional low-temperature condition means that all physical properties of the foam can still be basically maintained after the foam is placed for 7 days at the temperature of less than or equal to 80 ℃ and the humidity of less than or equal to 95 percent, and the polyurethane foam material can meet the requirements under the common condition because the processing condition is lower.
The hydrolysis stabilizer is usually added into polyester polyurethane materials, such as some elastomers and coating products, because ester groups are easy to generate the phenomenon of ester bond rupture to generate carboxylic acid groups under high humidity conditions for a long time, the carboxylic acid groups are easy to hydrolyze, and the hydrolysis stabilizer can effectively inhibit the reaction after being added, thereby playing a good stabilizing role. However, since the addition of the polyether urethane material has almost no significant effect, there is almost no patent in China.
Chinese patent CN107501508A discloses a waterproof hydrolysis-resistant soft foam polyurethane material, which comprises a soft foam polyurethane layer and a hydrophobic film layer, wherein a hydrolysis stabilizer is added in the process of preparing the soft foam polyurethane layer, and the hydrophobic film layer is matched to achieve better hydrolysis resistance, but the influence on the physical property of the foam material when the hydrolysis stabilizer is added is only compared, and no blank data is provided for comparison, so that the foam property is improved after the hydrolysis stabilizer is added.
Chinese patent CN103254386A discloses a preparation method of polyurethane semi-rigid foam composition, wherein the open cell ratio of the obtained foam is up to more than 90% by introducing a cell-opening agent, but the core density is lower than 25kg/m3, generally, the lower the density is, the more the amount of foaming agent water is, the more polyurea is generated after the reaction, the cell opening is facilitated, and in addition, the relevant experimental study on the hydrolysis stability is not carried out.
In general, when the core density of a polyurethane foam layer used for an automotive interior ceiling is 28-33 kg/m3, the tensile strength of the polyurethane foam layer is generally required to be more than or equal to 160kpa, the elongation at break is required to be more than or equal to 25%, and the compressive strength is required to be more than or equal to 100 kpa; when the tensile strength, elongation at break and compressive strength of the polyurethane foam layer satisfy the above requirements, the use of the polyurethane foam can satisfy the composite molding conditions of the automotive interior ceiling.
Disclosure of Invention
The invention aims to solve the technical problems of low aperture ratio and poor high-temperature high-humidity dimensional stability of polyurethane foam in the prior art, and provides novel high-aperture ratio hydrolysis-resistant polyurethane foam. The high-aperture-ratio hydrolysis-resistant polyurethane foam provided by the invention has the advantages of high aperture ratio and good high-temperature high-humidity dimensional stability. The second technical problem to be solved by the present invention is to provide a preparation method corresponding to the first technical problem. The present invention is also directed to a computer program product for solving the above-mentioned problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a high-aperture-ratio hydrolysis-resistant polyurethane foam comprises a component A and a component B, wherein the weight part ratio of the component A to the component B is 100: 130-170, the component A comprises 35-60 parts of polyether polyol I, 30-60 parts of polyether polyol II, 5-10 parts of chain extender, 1-3 parts of cross-linking agent, 0.1-1 part of reactive catalyst, 0.1-1 part of surfactant, 0.3-1.2 parts of pore-forming agent and 2.5-4 parts of water, and the component B comprises 30-70 parts of isocyanate, 30-50 parts of modified isocyanate and 5-20 parts of hydrolysis stabilizer;
wherein the polyether polyol I is one of glycerol, trimethylolpropane, ethanolamine or sorbitol as an initiator, and is ethylene oxide-propylene oxide copolymerized polyether polyol with the molecular weight of 5000-8000, and the primary hydroxyl content of the polyether polyol I is more than or equal to 70 percent;
the polyether polyol II is ethylene oxide polyether polyol taking at least one of glycerol, pentaerythritol, xylitol, sorbitol or sucrose as an initiator and having a molecular weight of 300-1000;
the chain extender is a non-amine micromolecular alcohol compound containing 2 functional groups; the cross-linking agent is an alcohol compound or an alcohol amine compound with 3 or 4 functionality; the reaction type catalyst is a tertiary amine catalyst containing hydroxyl; the surfactant is a polysiloxane-alkylene oxide block or graft copolymer; the cell opener is a polyoxyalkylene-polysiloxane type copolymer; the hydrolysis stabilizer in the component B is carbodiimide or epoxy compound.
In the technical scheme, preferably, the non-amine small molecular alcohol compound containing 2 functional groups is selected from at least one of 1,4 butanediol, ethylene glycol, diethylene glycol or neopentyl glycol, the alcohol compound containing 3 functional groups is selected from at least one of glycerol or trimethylolpropane, the alcohol compound containing 4 functional groups is selected from pentaerythritol, the alcohol amine compound is selected from diethanolamine or triethanolamine, the tertiary amine catalyst containing hydroxyl is selected from at least one of an intumescent tertiary amine catalyst, a gel tertiary amine catalyst or a balanced tertiary amine catalyst, the polysiloxane-oxyalkylene block copolymer is selected from at least one of B8526, B8544, AK 27 or L6915, the polysiloxane-oxyalkylene graft copolymer is selected from at least one of L5345, L629, B8534, B8444 or AK 5, the hydroxyl value of the polyoxyalkylene-polysiloxane copolymer is 1-4 mgKOH/g, the molecular weight is 2000-5000, the carbodiimide is selected from polycarbodiimide or monocarbodiimide, and the epoxy compound is selected from glycerol ether.
In the above technical solution, preferably, the polycarbodiimide is selected from at least one of S9000 or S11000, and the monocarbodiimide is selected from HM 1010; the glycidyl ether is at least one of GE100 or E500; the foaming tertiary amine catalyst is at least one selected from dimethylamino ethoxy ethanol, trimethyl hydroxyethyl ethylene diamine or N, N, N '-trimethyl-N' -hydroxyethyl bis-aminoethyl ether; the gel tertiary amine catalyst is selected from N, N-bis (dimethylaminopropyl) isopropanolamine or N- (dimethylaminopropyl) diisopropanolamine; the balanced tertiary amine catalyst is selected from dimethylethanolamine.
In the above technical solution, the isocyanate in component B is preferably selected from at least one of MDI-50, MIPS, S3051, PM200, 5005 or M20S; the modified isocyanate is selected from MM 103C.
In the above-mentioned embodiment, the polyoxyalkylene-polysiloxane type copolymer is preferably O501.
To solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the hydrolysis-resistant polyurethane foam with high open-cell rate comprises the following steps:
(1) according to the weight parts, 35-60 parts of polyether polyol I, 30-60 parts of polyether polyol II, 5-10 parts of chain extender, 1-3 parts of cross-linking agent, 0.1-1 part of reactive catalyst, 0.1-1 part of surfactant, 0.3-1.2 parts of pore-forming agent and 2.5-4 parts of water are stirred and mixed uniformly at the mixing and stirring temperature of 20-25 ℃ to obtain a mixed material A;
(2) adding 30-70 parts of isocyanate, 30-50 parts of modified isocyanate and 5-20 parts of hydrolysis stabilizer according to parts by weight to obtain a mixed material B;
(3) and quickly mixing and uniformly stirring the mixed material A and the mixed material B according to the weight part ratio of 100: 130-170, quickly injecting into a mold, and curing for 2-4 days after the free foaming is finished to obtain the high-aperture-ratio hydrolysis-resistant polyurethane foam.
In the technical scheme, the polyether polyol I is preferably one of glycerol, trimethylolpropane, ethanolamine or sorbitol as an initiator, and is ethylene oxide-propylene oxide copolymerized polyether polyol with the molecular weight of 5000-8000, wherein the primary hydroxyl content of the polyether polyol I is more than or equal to 70%;
the polyether polyol II is ethylene oxide polyether polyol taking at least one of glycerol, pentaerythritol, xylitol, sorbitol or sucrose as an initiator and having a molecular weight of 300-1000;
the chain extender is a non-amine micromolecular alcohol compound containing 2 functional groups; the cross-linking agent is an alcohol compound or an alcohol amine compound with 3 or 4 functionality; the reaction type catalyst is a tertiary amine catalyst containing hydroxyl; the surfactant is a polysiloxane-alkylene oxide block or graft copolymer; the cell opener is a polyoxyalkylene-polysiloxane type copolymer; the hydrolysis stabilizer in the component B is carbodiimide or epoxy compound.
In the technical scheme, preferably, the non-amine small molecular alcohol compound containing 2 functional groups is selected from at least one of 1,4 butanediol, ethylene glycol, diethylene glycol or neopentyl glycol, the alcohol compound containing 3 functional groups is selected from at least one of glycerol or trimethylolpropane, the alcohol compound containing 4 functional groups is selected from pentaerythritol, the alcohol amine compound is selected from diethanolamine or triethanolamine, the tertiary amine catalyst containing hydroxyl is selected from at least one of an intumescent tertiary amine catalyst, a gel tertiary amine catalyst or a balanced tertiary amine catalyst, the polysiloxane-oxyalkylene block copolymer is selected from at least one of B8526, B8544, AK 27 or L6915, the polysiloxane-oxyalkylene graft copolymer is selected from at least one of L5345, L629, B8534, B8444 or AK 5, the hydroxyl value of the polyoxyalkylene-polysiloxane copolymer is 1-4 mgKOH/g, the molecular weight is 2000-5000, the carbodiimide is selected from polycarbodiimide or monocarbodiimide, and the epoxy compound is selected from glycerol ether.
In the above technical solution, preferably, the polycarbodiimide is selected from at least one of S9000 or S11000, and the monocarbodiimide is selected from HM 1010; the glycidyl ether is at least one of GE100 or E500; the foaming tertiary amine catalyst is at least one selected from dimethylamino ethoxy ethanol, trimethyl hydroxyethyl ethylene diamine or N, N, N '-trimethyl-N' -hydroxyethyl bis-aminoethyl ether; the gel tertiary amine catalyst is selected from N, N-bis (dimethylaminopropyl) isopropanolamine or N- (dimethylaminopropyl) diisopropanolamine; the balanced tertiary amine catalyst is selected from dimethylethanolamine.
In the above technical solution, the isocyanate in component B is preferably selected from at least one of MDI-50, MIPS, S3051, PM200, 5005 or M20S; the modified isocyanate is selected from MM 103C.
In the above-mentioned embodiment, the polyoxyalkylene-polysiloxane type copolymer is preferably O501.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the high-aperture-ratio hydrolysis-resistant polyurethane foam is applied to an automotive interior ceiling.
According to the invention, carbodiimide or epoxy compound additives are adopted as hydrolysis stabilizers in a foaming system of the polyether polyurethane foam material, and are properly dissolved into a component B with extremely low viscosity, so that good solubility is obtained, and meanwhile, a polyoxyalkylene-polysiloxane type copolymer O501 is introduced into the component A as a cell opening agent, so that the size change rate of the prepared polyurethane foam is as low as 0.33% at the temperature of more than or equal to 120 ℃ and the humidity of more than or equal to 95%, the cell opening rate is as high as 95%, and good technical effects are obtained.
Detailed Description
The polyether polyols I and II used in the examples are as follows:
polyether polyol I:
polyether polyol I1: uses glycerin as initiator, and the polyether polyol copolymerized by epoxypropane and epoxyethane with molecular weight of 6000, and its primary hydroxyl group content is 72%.
Polyether polyol I2: trimethylolpropane is used as an initiator, and the primary hydroxyl content of polyether polyol copolymerized by propylene oxide and ethylene oxide with the molecular weight of 6000 is 70 percent.
Polyether polyol i 3: uses glycerine as initiator, and the polyether polyol copolymerized by epoxypropane and epoxyethane with molecular weight of 5000 has primary hydroxyl group content of 70%.
Polyether polyol i 4: the polyether polyol copolymerized by propylene oxide and ethylene oxide and taking ethanolamine as an initiator and having the molecular weight of 7600 has the primary hydroxyl content of 78 percent.
Polyether polyol I5: sorbitol is used as an initiator, and the primary hydroxyl content of polyether polyol copolymerized by propylene oxide and ethylene oxide with the molecular weight of 8000 is 80%.
Polyether polyol II:
polyether polyol IIA: uses glycerin as initiator and epoxy ethane polyether glycol with molecular weight of 380.
Polyether polyol IIB: pentaerythritol is used as an initiator, and ethylene oxide polyether polyol with the molecular weight of 450 is used.
Polyether polyol IIC: the ethylene oxide polyether polyol with the molecular weight of 1000 takes xylitol as an initiator.
Polyether polyol IID: sorbitol is used as an initiator, and ethylene oxide polyether polyol with the molecular weight of 400 is used.
Polyether polyol ie: the ethylene oxide polyether polyol with the molecular weight of 530 takes sucrose as an initiator.
TABLE 1 raw material List
Example 1
(1) Adding 1:47 parts of polyether polyol I, 40 parts of polyether polyol IIA and a chain extender EG: 6 parts of a crosslinking agent TMP: 1 part, reaction type catalyst PC 37: 0.3 part, surfactant B8534: 0.8 part, cell opener A: 1 part, water: 3.9 parts of the raw materials are uniformly stirred and mixed, and the mixing and stirring temperature is 20-25 ℃, so that a mixed material A is prepared;
(2) adding isocyanate M20S into a container II according to parts by weight: 50 parts of modified isocyanate MM 103C: 45 parts, hydrolysis stabilizer HM 1010: 5 parts of a mixed material B is prepared at a mixing and stirring temperature of 25 ℃;
(3) after the component A and the component B are quickly mixed and uniformly stirred according to the weight ratio of 100:130, the mixture is quickly injected into a prepared mould (2.4 × 1.5.5 1.5 × 1.2.2 m square mould), after free foaming is finished, curing is carried out for 3 days, high-aperture-ratio hydrolysis-resistant polyurethane foam is prepared, the conventional physical property detection data of the prepared high-aperture-ratio hydrolysis-resistant polyurethane foam is shown in a table 4, and the detection data of the prepared high-aperture-ratio hydrolysis-resistant polyurethane foam after being treated under the high-temperature and high-humidity conditions is shown in a table 5.
(4) The prepared hydrolysis-resistant polyurethane foam with high aperture ratio is applied to the automotive interior ceiling.
Examples 2 to 5
Examples 2 to 5 were carried out in accordance with the procedures of example 1, with the only difference being the type of the reaction raw material, the type of the catalyst, the mixture ratio of the raw materials, the reaction time and the temperature, as shown in Table 2, the conventional measured data of physical properties of the polyurethane foam with high open-cell content and hydrolysis resistance prepared are shown in Table 4, and the measured data of the polyurethane foam with high open-cell content and hydrolysis resistance prepared under the high-temperature and high-humidity conditions are shown in Table 5; the prepared hydrolysis-resistant polyurethane foam with high aperture ratio is applied to the automotive interior ceiling.
Table 2 parts by weight of raw materials for each component in examples 1 to 5 and comparative examples 1 to 2
Examples 6 to 10
Examples 6 to 10 experiments were carried out according to the procedures of example 1, with the only difference being the type of the reaction raw material, the type of the catalyst, the mixture ratio of the raw materials, the reaction time and the temperature, as shown in Table 3, the conventional measured data of physical properties of the polyurethane foam with high open-cell content and hydrolysis resistance prepared are shown in Table 4, and the measured data of the polyurethane foam with high open-cell content and hydrolysis resistance prepared under the high-temperature and high-humidity conditions are shown in Table 5; the prepared hydrolysis-resistant polyurethane foam with high aperture ratio is applied to the automotive interior ceiling.
Table 3 parts by weight of raw materials for each component in example 6 to example 10 and comparative example 3
Comparative example 1
The procedure was followed as in example 1 except that no hydrolysis stabilizer was added to component B in order to investigate the effect of the presence of the hydrolysis stabilizer on the physical properties of the polyether polyurethane foam under high temperature and high humidity conditions, as shown in Table 2, and the data of the prepared polyurethane foam on the measurement of the conventional physical properties are shown in Table 4 and the data of the prepared polyurethane foam after the treatment under high temperature and high humidity conditions are shown in Table 5.
Comparative example 2
The procedure was followed in example 1 except that the polyether polyurethane foam obtained was treated under different test conditions for the purpose of investigating the influence of the foam properties under conventional low-temperature conditions of the polyether polyurethane foam to which the hydrolysis stabilizer was added, as shown in Table 2, and the measurement data of the conventional property quality of the prepared polyurethane foam are shown in Table 4 and the measurement data of the polyurethane foam after the treatment under conventional low-temperature conditions are shown in Table 6.
Comparative example 3
(1) According to parts by weight, 90 parts of polyester polyol (with the functionality of 2 and the hydroxyl value of 60mgKOH/g) and a crosslinking agent EG: 8 parts, reaction catalyst Dabco EG: 0.3 part; surfactant Dabco DC 193: 0.2 part, water: 0.5 part, sodium perchlorate: 1 part, stirring and mixing uniformly at the temperature of 45 ℃ to prepare a component A;
(2) adding isocyanate M20S into a container IV according to the parts by weight: 90 parts, hydrolysis stabilizer S9000: 10 parts of the components B are prepared at the mixing and stirring temperature of 40 ℃;
(3) and (3) rapidly mixing and uniformly stirring the component A and the component B according to the weight part ratio of 100:130, quickly injecting the mixture into a prepared mould (200 x 10mm square mould), closing the mould, curing for 5min, and demoulding and curing for 3 days to obtain the polyurethane elastomer material.
The purpose is to study the influence of physical properties of the polyester polyurethane material introduced with the hydrolysis stabilizer under the conventional low temperature conditions, specifically shown in table 3, the conventional physical property quality detection data of the prepared polyurethane elastomer material is shown in table 4, and the detection data of the polyurethane elastomer material after being treated under the conventional low temperature conditions is shown in table 6.
Comparative example 4
The procedures of comparative example 3 were followed, with the only difference that the obtained polyester polyurethane material was treated under different test conditions in order to investigate the influence of the physical properties of the polyester polyurethane material added with a hydrolysis stabilizer under high temperature and high humidity conditions, specifically, as shown in Table 3, the data of the quality test of the conventional physical properties of the polyurethane elastomer material prepared is shown in Table 4, and the data of the test of the polyurethane elastomer material prepared after the treatment under the conventional low temperature conditions is shown in Table 6.
TABLE 4 data for conventional measurement of physical properties of polyurethane materials obtained in examples 1 to 10 and comparative examples 1 to 4
Remarking: the conventional physical properties refer to physical data detected at the normal temperature of 20-25 DEG C
TABLE 5 data of physical properties detection of polyurethane materials obtained in examples 1 to 10 and comparative examples 1 and 4 after treatment under high temperature and high humidity conditions
Remarking: the high temperature and high humidity treatment condition is that the sample is placed at 120 ℃ and 100% humidity for 5h, taken out and dried at 70 ℃ for 3h, and the test is carried out after 3 times of circulation.
TABLE 6 data for measuring physical properties of polyurethane materials obtained in comparative examples 2 to 3 after treatment under conventional low-temperature conditions
Remarking: the conventional low-temperature treatment condition is that the mixture is placed at 70 ℃ and 95% humidity for 7d and is taken out for testing.
As can be seen from the table:
comparing examples 1 to 10 of tables 4 and 5, it can be seen that the physical properties of the polyurethane materials of examples 1 to 10 after treatment under high temperature and high humidity conditions are all kept good, and the dimensional stability is less than 1%;
comparing tables 4 and 5, it can be seen that in example 1 and comparative example 1, the physical properties of the composition are greatly changed and the dimensional change rate is more than 3% after the composition is treated under high temperature and high humidity conditions in the absence of hydrolysis stabilizer;
comparing example 1 and comparative example 2 in tables 4,5 and 6, it can be seen that the two different treatment conditions have less influence on the physical properties of the polyurethane foam;
comparing example 1 and comparative examples 3 and 4 in tables 4,5 and 6, it can be seen that the effect of the hydrolysis stabilizer on the polyether polyurethane material obtained in the present invention is superior to that of the conventional polyester polyurethane material.
Claims (7)
1. A high-aperture-ratio hydrolysis-resistant polyurethane foam comprises a component A and a component B, wherein the weight part ratio of the component A to the component B is 100: 130-170, the component A comprises 35-60 parts of polyether polyol I, 30-60 parts of polyether polyol II, 5-10 parts of chain extender, 1-3 parts of cross-linking agent, 0.1-1 part of reactive catalyst, 0.1-1 part of surfactant, 0.3-1.2 parts of pore-forming agent and 2.5-4 parts of water, and the component B comprises 30-70 parts of isocyanate, 30-50 parts of modified isocyanate and 5-20 parts of hydrolysis stabilizer;
wherein the polyether polyol I is at least one of glycerol, trimethylolpropane, ethanolamine or sorbitol as an initiator, and is ethylene oxide-propylene oxide copolymerized polyether polyol with the molecular weight of 5000-8000, and the primary hydroxyl content of the polyether polyol I is more than or equal to 70 percent;
the polyether polyol II is ethylene oxide polyether polyol taking at least one of glycerol, pentaerythritol, xylitol, sorbitol or sucrose as an initiator and having a molecular weight of 300-1000;
the chain extender is a non-amine micromolecular alcohol compound containing 2 functional groups; the cross-linking agent is an alcohol compound or an alcohol amine compound with 3 or 4 functionality; the reaction type catalyst is a tertiary amine catalyst containing hydroxyl; the surfactant is a polysiloxane-alkylene oxide block or graft copolymer; the cell opener is a polyoxyalkylene-polysiloxane type copolymer; the hydrolysis stabilizer in the component B is carbodiimide or epoxy compound.
2. The polyurethane foam with high open-cell rate and hydrolysis resistance as claimed in claim 1, wherein the non-amine small molecular alcohol compound with 2 functional groups is at least one selected from 1,4 butanediol, ethylene glycol, diethylene glycol or neopentyl glycol, the alcohol compound with 3 functional groups is at least one selected from glycerol or trimethylolpropane, the alcohol compound with 4 functional groups is pentaerythritol, the alcohol amine compound is diethanolamine or triethanolamine, the tertiary amine catalyst with hydroxyl group is at least one selected from foaming tertiary amine catalyst, gel tertiary amine catalyst or balanced tertiary amine catalyst, the polysiloxane-oxyalkylene block copolymer is at least one selected from B8526, B8544, AK8827 or 8669124 5, the polysiloxane-oxyalkylene graft copolymer is at least one selected from 365332, L629, B8534, B8444 or AK mg8805, the hydroxyl value of the polyoxyalkylene-polysiloxane copolymer is 1-4 KOH/g, the molecular weight is 2000-5000, the carbodiimide is carbodiimide selected from carbodiimide or the monoglycidyl ether compound is selected from glycidyl ether compounds.
3. The high open-cell, hydrolysis-resistant polyurethane foam of claim 3, wherein the polycarbodiimide is selected from at least one of S9000 or S11000, and the monocarbodiimide is selected from HM 1010; the glycidyl ethers are selected from at least one of GE100 or GE 500; the foaming tertiary amine catalyst is at least one selected from dimethylamino ethoxy ethanol, trimethyl hydroxyethyl ethylene diamine or N, N, N '-trimethyl-N' -hydroxyethyl bis-aminoethyl ether; the gel tertiary amine catalyst is selected from N, N-bis (dimethylaminopropyl) isopropanolamine or N- (dimethylaminopropyl) diisopropanolamine; the balanced tertiary amine catalyst is selected from dimethylethanolamine.
4. The high open-cell hydrolysis-resistant polyurethane foam of claim 1, wherein the isocyanate in component B is selected from at least one of MDI-50, MIPS, S3051, PM200, 5005 or M20S; the modified isocyanate is selected from MM 103C.
5. The high open-cell, hydrolysis-resistant polyurethane foam of claim 1, wherein the polyoxyalkylene-polysiloxane type copolymer is O501.
6. The method of claim 1, comprising the steps of:
(1) according to the weight parts, 35-60 parts of polyether polyol I, 30-60 parts of polyether polyol II, 5-10 parts of chain extender, 1-3 parts of cross-linking agent, 0.1-1 part of reactive catalyst, 0.1-1 part of surfactant, 0.3-1.2 parts of pore-forming agent and 2.5-4 parts of water are stirred and mixed uniformly at the mixing and stirring temperature of 20-25 ℃ to obtain a mixed material I;
(2) adding 30-70 parts of isocyanate, 30-50 parts of modified isocyanate and 5-20 parts of hydrolysis stabilizer according to parts by weight to obtain a mixed material II;
(3) and quickly mixing and uniformly stirring the mixed material I and the mixed material II according to the weight part ratio of 100: 130-170, quickly injecting into a mold, and curing for 2-4 days after the free foaming is finished to obtain the high-aperture-ratio hydrolysis-resistant polyurethane foam.
7. The high open-cell hydrolysis-resistant polyurethane foam of claim 1 applied to an automotive interior ceiling.
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