CN104710596A

CN104710596A - Polyurethane foam composition, polyurethane foam and preparation method of polyurethane foam

Info

Publication number: CN104710596A
Application number: CN201510043868.4A
Authority: CN
Inventors: 韩海军
Original assignee: Beijing Oriental Yuhong Waterproof Technology Co Ltd
Current assignee: Beijing Oriental Yuhong Waterproof Technology Co Ltd
Priority date: 2015-01-28
Filing date: 2015-01-28
Publication date: 2015-06-17

Abstract

The invention provides a polyurethane composition, a polyurethane foam and a preparation method of the polyurethane foam. A problem of polyurethane foams in the prior art cannot be used in wood imitation. The polyurethane foam has a finely porous structure, has much higher density than rigid polyurethane foam, and has high tensile strength, compressive strength, impact strength and bending strength; the above wood imitation rigid foam polyurethane material has compact, tough and smooth skins, and realizes difficult scratches while in use; and the material can be used as a large strength and small density imitation wood material to make various colors of modern fashionable home finishing, and can also be used in the fields of insulation materials, heat insulation materials, structure materials, sound insulation materials, and aviation and spaceflight materials.

Description

Polyurethane foam composition, polyurethane foam and preparation method thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a polyurethane foam composition, polyurethane foam and a preparation method thereof.

Background

The application of the wood is wide, but in recent years, due to the fact that excessive exploitation of forest resources causes deterioration of ecological environment and water and soil loss, some countries control the development of natural forestry resources and stop excessive chopping. At present, the research and development of wood-like materials become a hot topic. In the field of traditional wood applications, metal materials and wood-like materials have partially replaced wood, such as wooden furniture, doors and windows, appliance housings, wooden tubs, carved decorative devices, mirror frames, and the like. Most synthetic woods can be nailed, planed and sawed, have similar appearance, hand feeling and density as the woods, can also be dampproof, mothproof and flame retardant, do not need paint and the like, and are superior to the woods in whole.

There are many kinds of raw materials for synthetic wood, which are generally molded with inorganic or organic fillers and binders. The resin used for the wood-like material is common resin such as polyethylene, polyester, polyurethane, polystyrene, acrylonitrile-butadiene-styrene copolymer and the like, the organic filler is natural fiber (such as straw, straws, grass, hemp, bamboo filament and other agricultural byproduct fragments), and the inorganic filler is calcium carbonate, stone powder and the like. The popularization of replacing wood with plastic, especially changing waste into valuable and comprehensively utilizing, can save wood and protect resource environment.

There are few wood-like materials such as high-density concrete, steel, etc. whose exterior has a wood grain or bark structure only by coating or molding processes, and are not really synthetic wood as a decorative material or a handrail, etc.

Disclosure of Invention

The technical scheme adopted for solving the problems is that the polyurethane composition comprises a component A and a component B, wherein the component A comprises: polyphenyl polymethylene polyisocyanates;

the component B comprises: polyether polyol, polyester polyol, a foam stabilizer, a hydrolysis stabilizer, a foaming agent, a catalyst, a flame retardant and a crosslinking agent.

Wherein, the mass fraction of NCO in the component A is 30.1-32.5%, and the functionality is more than 2.

The polyphenyl polymethylene polyisocyanate is one or more selected from M20S, PM-200, SUP-5005J and 44V 20.

Among them, polyphenyl polymethylene polyisocyanate has a functionality of more than 2, and the resulting polyurethane foam has a relatively good stress property.

Preferably, the component B comprises the following components in parts by mass:

60-70 parts of polyether polyol, 30-40 parts of polyester polyol, 1-3 parts of foam stabilizer, 0.1-0.6 part of hydrolysis stabilizer, 1-10 parts of foaming agent, 0.1-1.5 parts of catalyst, 5-15 parts of flame retardant and 1-2.5 parts of cross-linking agent.

Preferably, the polyether polyol is selected from one or two of polyoxyalkylene polyol and polytetrahydrofuran polyol. The functional polyurethane material is prepared by ring-opening polymerization of propylene oxide, ethylene oxide and tetrahydrofuran by taking glycerol (glycerol), trimethylolpropane, 1, 2, 6-hexanetriol, triethanolamine, pentaerythritol, sorbitol, mannitol, sucrose and the like as initiators, wherein the functionality is 3-6;

preferably, the polyoxyalkylene polyol is selected from one or more of YD-4110, TAE-300, TEP-3033, TEP-240, MN-3050 and MN-3050D, EP-330N.

Preferably, the polytetrahydrofuran polyol is one or two of TNR-410 and THS-700A.

The addition of polyether polyol results in high hydrolysis resistance and low cost of polyurethane foam.

Preferably, the polyester polyol is selected from one or more of alkyd polyester polyol, poly-caprolactone polyol, polycarbonate polyol and rosin polyester polyol.

Preferably, the alkyd polyester polyol is selected from one or more of CDX-218, CMA1044, MX-355, MX-785, MX-706, MX-2325, YA-7210, YA-7220, YA-7410 and YA-7120.

Preferably, the poly-caprolactone polyol is selected from one or both of L205AL, 210 CP.

Preferably, the polycarbonate polyol is selected from one or two of ST-602 and ST-615.

Preferably, the rosin polyester Polyol is selected from one or two of Niax Polyol-D540 and Niax Polyol-D560.

Wherein, the polyester polyol has a benzene ring structure and can improve the stress intensity of the prepared polyurethane foam.

Preferably, the foam stabilizer is selected from one or more of BYK-8020, B8454, B8863Z, B8642, B8525, B8476, L5440, L6900, L6863, SD-111, SD-211, SD-511, SD-622, AK8830, AK8818 and AK 8801.

The addition of the foam stabilizer can ensure that the prepared polyurethane foam has uniform particle size, and simultaneously, the compatibility of the other components can be adjusted according to the selection of the foam stabilizers with different polarities.

Preferably, the hydrolysis stabiliser comprises a carbodiimide. The hydrolysis stabilizer is used for inhibiting hydrolysis of polyester polyol and improving storage performance of the polyurethane composition.

Preferably, the carbodiimide is selected from one or more of Stabilizer-7000, Stabaxol-1, Stabaxol-p and BIOSW-100.

Preferably, the blowing agent comprises a physical blowing agent or a chemical blowing agent;

the physical foaming agent is selected from one or more of HCFC-141b, pentane and HFC-365 mfc.

The chemical blowing agent includes water.

The blowing agent is used to react to produce a foam or to produce bubbles by endothermic expansion.

Preferably, the catalyst comprises one or more selected from dimethylethanolamine, triethylenediamine, triethylamine, pentamethyldipropylenetriamine, and trimethylhydroxyethylethylenediamine.

Preferably, the flame retardant is selected from one or more of dimethyl methyl phosphate, tris (2-chloroisopropyl) phosphate and tris (2-chloroethyl) phosphate.

Preferably, the flame retardant is selected from one or more of Antiblaze BK-69, Antiblaze FL-76 and XF-688.

Preferably, the cross-linking agent is selected from one or more of triethanolamine, trimethylolpropane and 3, 3-dichloro-4, 4-diaminodiphenylmethane. The cross-linking agent reacts with the polyphenyl polymethylene polyisocyanate to generate a net structure, so that the strength of the polyurethane foam is enhanced.

The component B can also be added with pigment, for example, the pigment can be one or more of red paste B, blue paste HG, yellow paste HR, white paste KE5086, green paste 51004, purple paste 502082 and black paste NT01, and the weight of the pigment is 0.1-1.0 part by mass.

The invention also provides polyurethane foam, the polyurethane foam is prepared by foaming the polyurethane foam composition,

the invention also provides a preparation method of the polyurethane foam, which comprises the following steps;

foaming and curing the polyurethane foam composition at 15-45 ℃ for 20-40min to obtain polyurethane foam

The polyurethane foam composition, the polyurethane foam and the preparation method thereof provided by the invention have a micro-pore structure, have much higher density than that of conventional rigid polyurethane foam for heat insulation, and have higher tensile strength, compressive strength, impact strength and bending strength. In addition, the wood-like hard foam polyurethane material has compact, tough and smooth surface skin, and is not easy to scratch when in use. The wood-like material can be used as a wood-like material with higher strength and lower density to manufacture modern fashionable homes with various colors, and can also be used in the fields of insulating materials, heat insulation materials, structural materials, sound insulation materials, aviation and aerospace materials and the like.

Detailed Description

In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will be further described in detail with reference to the following detailed description.

Example 1:

this example provides a polyurethane foam composition comprising an a-side and a B-side, wherein the a-side comprises: polyphenyl polymethylene polyisocyanates;

the component B comprises: polyether polyol, polyester polyol, a foam stabilizer, a hydrolysis stabilizer, a foaming agent, a catalyst, a flame retardant, a crosslinking agent and pigment.

The components of the component B and the parts by mass of each component are shown in Table 1.

The preparation method of the component B comprises the following steps:

adding a foam stabilizer, a hydrolysis stabilizer, a foaming agent, a catalyst, a flame retardant, a cross-linking agent and a pigment into polyol according to the mass parts in the table 1, and stirring for 60min by an electric stirrer at the rotating speed of 200r/min to obtain a component B mixed solution.

This example also provides a polyurethane foam and a method of making the same:

mixing the component A and the component B in a mass ratio such that the molar ratio of-NCO groups in the component A to hydroxyl groups in the component B is equal.

Specifically, A, B two components are mixed, stirred at a high speed of 250r/min for 4s, foamed and cured at 15 ℃ for 40min, and the polyurethane foam material is obtained after curing. Then, after the film was cured for 48 hours under standard conditions (temperature 23. + -. 2 ℃ C., relative humidity 50. + -. 10%), the performance was tested, and the test results are shown in Table 2:

wherein,

the density was measured according to the method or standard GB/T6343-2009 determination of apparent density of foams and rubbers.

The compression strength is tested according to the method or standard GB/T8813 & 2008 & determination of compression Properties of rigid foams.

The flexural strength was tested according to the method or standard GB/T8812.1-2007 determination of flexural Properties of rigid foams.

The impact strength was tested according to the method or standard for the test of impact properties described in GB/T13525-1992 test method for tensile impact Properties of plastics.

Tensile strength was tested according to the method or standard of GB/T9641-1988 method for testing tensile Properties of rigid foams.

The oxygen index is tested according to the method or standard of GB/T2406.2-2009 'determination of combustion behavior by oxygen index method for plastics'.

Example 2:

this example provides a polyurethane composition comprising an a-side and a B-side, wherein the a-side comprises: polyphenyl polymethylene polyisocyanates;

The preparation method of the component B comprises the following steps:

This example also provides a polyurethane foam and a method of making the same:

Specifically, A, B two components are mixed, stirred at a high speed of 250r/min for 3s, foamed and cured for 20min at 45 ℃ to obtain the polyurethane foam material. Then, after the film was cured for 48 hours under standard conditions (temperature 23. + -. 2 ℃ C., relative humidity 50. + -. 10%), the performance was measured, and the results are shown in Table 2.

Example 3:

The preparation method of the component B comprises the following steps:

This example also provides a polyurethane foam and a method of making the same:

Specifically, A, B two components are mixed, stirred at a high speed of 250r/min for 5s, foamed and cured at 20 ℃ for 35min, and the polyurethane foam material is obtained after curing. Then, after the film was cured for 48 hours under standard conditions (temperature 23. + -. 2 ℃ C., relative humidity 50. + -. 10%), the performance was measured, and the results are shown in Table 2.

Example 4:

The preparation method of the component B comprises the following steps:

This example also provides a polyurethane foam and a method of making the same:

Specifically, A, B two components are mixed, stirred at a high speed of 250r/min for 4s, foamed and cured for 30min at 35 ℃, and the polyurethane foam material is obtained after curing. Then, after the film was cured for 48 hours under standard conditions (temperature 23. + -. 2 ℃ C., relative humidity 50. + -. 10%), the performance was measured, and the results are shown in Table 2.

Table 1 components and parts by mass of each component of the polyurethane composition in each example

TABLE 2 Performance test results for polyurethane foams prepared in the examples of the present invention

Detecting items	Example 1	Example 2	Example 3	Example 4
					Density/(kg/m)³)	210	180	198	205
Compressive Strength/(MPa) (deformation 10%)	12.5	10.3	11.5	12.1
					Flexural Strength/MPa	13	11	11.6	12
Impact Strength/(KJ/m)²)	20	17	18.3	19
					Tensile strength/MPa	15	12	13.7	14
Oxygen index (%)	26.1	26.0	26.1	26.0

Note: an oxygen index greater than 26 indicates a non-flammability under normal air conditions.

As can be seen from Table 2, the polyurethane composition, the polyurethane foam and the preparation method thereof provided by the invention have a micro-pore structure, have a much higher density than that of the conventional rigid polyurethane foam for heat insulation, and have higher tensile strength, compressive strength, impact strength and bending strength. In addition, the wood-like hard foam polyurethane material has compact, tough and smooth surface skin, and is not easy to scratch when in use. The wood-like material can be used as a wood-like material with higher strength and lower density to manufacture modern fashionable homes with various colors, and can also be used in the fields of insulating materials, heat insulation materials, structural materials, sound insulation materials, aviation and aerospace materials and the like.

It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.

Claims

1. A polyurethane foam composition comprising an a-side and a B-side, wherein the a-side comprises: polyphenyl polymethylene polyisocyanates;

2. The polyurethane foam composition of claim 1, wherein the polyphenyl polymethylene polyisocyanate is selected from one or more of M20S, PM-200, SUP-5005J, 44V 20.

3. The polyurethane foam composition of claim 1, wherein the B component comprises, in parts by mass:

4. The polyurethane foam composition of claim 1, wherein the polyether polyol is selected from one or both of a polyoxyalkylene polyol and a polytetrahydrofuran polyol.

5. The polyurethane foam composition of claim 4, wherein the polyoxyalkylene polyol is selected from one or more of YD-4110, TAE-300, TEP-3033, TEP-240, MN-3050D, EP-330N.

6. The polyurethane foam composition of claim 4, wherein the polytetrahydrofuran polyol is selected from one or both of TNR-410, THS-700A.

7. The polyurethane foam composition of claim 1, wherein the polyester polyol is selected from one or more of alkyd polyester polyol, poly-caprolactone polyol, polycarbonate polyol, and rosin polyester polyol.

8. The polyurethane foam composition of claim 7, wherein the alkyd polyester polyol is selected from one or more of CDX-218, CMA1044, MX-355, MX-785, MX-706, MX-2325, YA-7210, YA-7220, YA-7410, YA-7120.

9. The polyurethane foam composition of claim 7, wherein the poly-caprolactone polyol is selected from one or both of L205AL and 210 CP.

10. The polyurethane foam composition of claim 7, wherein the polycarbonate polyol is selected from one or both of ST-602 and ST-615.

11. The polyurethane foam composition of claim 7, wherein the rosin polyester Polyol is selected from one or both of Niax Polyol-D540, Niax Polyol-D560.

12. The polyurethane foam composition according to claim 1, wherein the foam stabilizer is selected from one or more of BYK-8020, B8454, B8863Z, B8642, B8525, B8476, L5440, L6900, L6863, SD-111, SD-211, SD-511, SD-622, AK8830, AK8818, and AK 8801.

13. The polyurethane foam composition of claim 1, wherein the hydrolysis stabilizer comprises a carbodiimide.

14. The polyurethane foam composition of claim 13, wherein the carbodiimide is selected from the group consisting of Stabilizer-7000, Stabaxol-1, Stabaxol-p, and BIOSW-100.

15. The polyurethane foam composition of claim 1, wherein the blowing agent comprises a physical blowing agent or a chemical blowing agent;

the physical foaming agent is selected from one or more of HCFC-141b, pentane and HFC-365 mfc;

the chemical blowing agent includes water.

16. The polyurethane foam composition of claim 1, wherein the catalyst comprises one or more selected from the group consisting of dimethylethanolamine, triethylenediamine, triethylamine, pentamethyldipropylenetriamine, and trimethylhydroxyethylethylenediamine.

17. The polyurethane foam composition of claim 1, wherein the flame retardant is selected from one or more of dimethyl methylphosphonate, tris (2-chloroisopropyl) phosphate, and tris (2-chloroethyl) phosphate.

18. The polyurethane foam composition of claim 17, wherein the flame retardant is selected from one or more of Antiblaze BK-69, Antiblaze FL-76, XF-688.

19. The polyurethane foam composition of claim 1, wherein the crosslinker is selected from one or more of triethanolamine, trimethylolpropane, and 3, 3-dichloro-4, 4-diaminodiphenylmethane.

20. A polyurethane foam prepared by foaming the polyurethane foam composition of any one of claims 1-19.

21. A method for preparing polyurethane foam, characterized by comprising the following steps;

foaming and curing a polyurethane foam composition according to any one of claims 1-19 at a temperature of 15-45 ℃ for 20-40min to obtain a polyurethane foam.