CN113896860B - Full-water polyurethane rigid foam material, preparation method and application - Google Patents
Full-water polyurethane rigid foam material, preparation method and application Download PDFInfo
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Abstract
The invention discloses a full-water polyurethane rigid foam material, which comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 60-90 parts of polyether polyol; 10-40 parts of polyester polyol; 2-6 parts of a foam stabilizer; 0.05-0.4 part of amine catalyst; 0.05-0.5 part of metal catalyst; 2-10 parts of a trimerization catalyst; 2-6 parts of a foaming agent; the component B comprises the following components in parts by weight: 200-280 parts of isocyanate. The functionality of the polyether polyol is 4-5, the hydroxyl value is 420-480mgKOH/g, the viscosity is 2000-4000mPa.s, and the water content is less than 0.1%; the functionality of the polyester polyol is 5-7, the hydroxyl value is 380-420mgKOH/g, the viscosity is 2500-4000mPa.s, and the water content is less than 0.1%; the foaming agent is water. The low-density polyurethane rigid foam product prepared by the invention has the advantages of uniform and fine foam, fine foam hole, and excellent compression strength and compression modulus performance.
Description
Technical Field
The invention relates to the field of polyurethane rigid foam, in particular to a full-water polyurethane rigid foam material, a preparation method and application thereof.
Background
The polyurethane rigid foam is an important high-molecular synthetic material, and has excellent physical and mechanical properties, chemical resistance and unique excellent processing formability. Generally, the rigid polyurethane foam can be prepared by reacting two components of isocyanate and combined polyether, and the combined polyether generally comprises polyether polyol, a foaming agent, a catalyst and the like.
At present, the most used foaming agent is fluorine-chlorine hydrocarbon, which can destroy the earth ozone layer substance and cause global climate deterioration, and the high importance of countries in the world is aroused. Foaming techniques with zero ozone depletion are becoming more and more popular.
Full water foaming is a technique of foaming a polyurethane substrate to form a foam by using carbon dioxide gas generated by the reaction of isocyanate with water as a foaming agent. The chlorofluorocarbon foaming agent is not used in the process, so that the ozone layer is not damaged, and the method is an ideal chlorofluorocarbon foaming substitution technology.
However, the use of water as a hard foam blowing agent has the disadvantage that the presence of polyurea makes the foam brittle and the strength decreases, since water and isocyanate form carbon dioxide bubbles and also form large amounts of polyurea.
Particularly, when the low-density rigid polyurethane foam product is produced, water is used as a rigid foam foaming agent, so that the foam is crisp, the strength is poor, and the foam holes are thick, uneven and uneven, so that the development and the application of the rigid polyurethane foam product are limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a full-water polyurethane rigid foam material and a preparation method thereof, and a low-density polyurethane rigid foam product prepared from the full-water polyurethane rigid foam material has uniform and fine foam, fine foam pores (the pore size is about 150 microns), and excellent compressive strength and compressive modulus performance.
In order to realize the purpose of the invention, the adopted technical scheme is as follows:
the full-water polyurethane rigid foam material comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 100
Wherein, the component A comprises the following components in parts by weight:
wherein, the component B comprises the following components in parts by weight:
200-280 parts of isocyanate.
The functionality of the polyether polyol is 4-5, the hydroxyl value is 420-480mgKOH/g, the viscosity is 2000-4000mPa.s, and the water content is less than 0.1%;
the functionality of the polyester polyol is 5-7, the hydroxyl value is 380-420mgKOH/g, the viscosity is 2500-4000mPa.s, and the water content is less than 0.1%;
the foaming agent is water.
In a preferred embodiment of the invention, the polyether polyol is a product based on the reaction of an octafunctional sucrose with a trifunctional glycerol as initiator.
In a preferred embodiment of the present invention, the polyester polyol is a product prepared based on the reaction of tetrafunctional pyromellitic dianhydride with butanediol.
In a preferred embodiment of the present invention, the foam stabilizer is a polysiloxane-polyoxyalkylene ether block copolymer.
In a preferred embodiment of the present invention, the amine catalyst is a high activity gel catalyst, preferably triethylenediamine. High activity means activity at 1 x 10 -3 g·mol -1 ·min -1 The above.
In a preferred embodiment of the present invention, the metal catalyst is an organotin-based catalyst, preferably stannous octoate or dibutyltin dilaurate.
In a preferred embodiment of the present invention, the trimerisation catalyst is a delayed action catalyst, preferably a phenol amine catalyst.
In a preferred embodiment of the invention, the isocyanate is a polyphenyl polymethylene isocyanate having an NCO content of 30-32%.
A preparation method of a full-water polyurethane rigid foam material comprises the following steps:
s1, uniformly mixing polyether polyol, polyester polyol, a foam stabilizer, an amine catalyst, a metal catalyst, a trimerization catalyst and a foaming agent to obtain a first mixture;
s2, adding the isocyanate into the first mixture and uniformly mixing to obtain a second mixture;
and S3, pouring the second mixture into a mold for foaming, demolding after the foam is solidified, and curing to obtain the all-water polyurethane hard foam material.
In a preferred embodiment of the invention, the stirring speed in the step S1 is 200-3000r/min, and the stirring time is 5-10min;
the stirring speed in the step S2 is 200-3000r/min, and the stirring time is 10-15S;
the curing in the step S3 is to be placed for 4 to 7 days at room temperature or to be placed in an oven at the temperature of 90 ℃ for 4 to 7 hours.
The application of the all-water polyurethane rigid foam material is to use the all-water polyurethane rigid foam material as a structural material for supporting and filling.
The preferred application is in the manufacture of wind power foam core materials.
The invention has the beneficial effects that:
firstly, the full-water polyurethane rigid foam material provided by the invention effectively improves the compression strength and the compression modulus of rigid foam products by selecting polyether polyol and polyester polyol with special structures for compounding and adopting a proper trimerization catalyst.
Secondly, the fully aqueous polyurethane rigid foam material provided by the invention can meet the operation time requirement of manual foaming by adjusting the proportion of the three catalysts.
Thirdly, the full-water polyurethane rigid foam material provided by the invention enables the rigid foam product to have uniform and fine pores, small pore diameter and uniform density by selecting proper amounts of the foam stabilizer and the foaming agent.
Fourthly, the preparation method of the full-water polyurethane rigid foam provided by the invention has very simple steps, only needs to mix according to a proportion, and is simple and easy to implement.
Detailed Description
The following detailed description of the preferred embodiments of the invention is provided to enable those skilled in the art to better understand the advantages and features of the invention.
Example 1:
the embodiment provides a full water polyurethane rigid foam, which comprises the following raw materials:
the component A comprises:
polyether polyol RF4110A 70g,
30g of PES (polyester polyol) 504 g,
a foam stabilizer SD201 g,
0.1g of the amine-based catalyst A,
0.15g of the metal catalyst T9,
trimerization catalyst TMR 2g, water 4g.
The component B comprises:
polyphenyl polymethylene isocyanate PM200 g.
The preparation method of the all-water polyurethane rigid foam comprises the following steps:
s1, accurately weighing the component A according to the weight in the formula, putting the component A into a cup, and stirring for 5min at a speed of 300r/min to obtain a first mixture;
s2, adding the isocyanate component B into the first mixture, and stirring for 12S at 1000r/min to obtain a second mixture;
and S3, pouring the second mixture into a mold for foaming, demolding after the foam is solidified, and curing in an oven at 90 ℃ for 6 hours to obtain the full-water polyurethane hard foam material.
Example 2:
the embodiment provides a full-water polyurethane rigid foam which comprises the following raw materials:
the component A comprises:
polyether polyol RF4110A 90g,
PES504 g of polyester polyol is 10g,
a foam stabilizer SD201 g,
0.1g of the amine-based catalyst A,
0.15g of the metal catalyst T12,
trimerization catalyst TMR 2g, water 4g.
The component B comprises:
polyphenyl polymethylene isocyanate PM200 g.
The preparation method of the full-water polyurethane rigid foam comprises the following steps:
s1, accurately weighing the component A according to the weight in the formula, putting the component A into a cup, and stirring for 5min at a speed of 500r/min to obtain a first mixture;
s2, adding the isocyanate component B into the first mixture, and stirring for 12S at 1000r/min to obtain a second mixture;
and S3, pouring the second mixture into a mold for foaming, demolding after the foam is solidified, and curing in an oven at 90 ℃ for 6 hours to obtain the full-water polyurethane rigid foam material.
Example 3:
the embodiment provides a full-water polyurethane rigid foam which comprises the following raw materials:
the component A comprises:
polyether polyol RF4110A 70g,
30g of PES (polyester polyol) 504 g,
a foam stabilizer SD201 4g,
0.1g of the amine-based catalyst A,
0.15g of the metal catalyst T12,
trimerization catalyst TMR 2g, water 4g.
The component B comprises:
polyphenyl polymethylene isocyanate PM200 g.
The preparation method of the all-water polyurethane rigid foam comprises the following steps:
s1, accurately weighing the component A according to the weight in the formula, putting the component A into a cup, and stirring for 5min at a speed of 500r/min to obtain a first mixture;
s2, adding the isocyanate as the component B into the first mixture, and stirring for 12S at 1000r/min to obtain a second mixture;
and S3, pouring the second mixture into a mold for foaming, demolding after the foam is solidified, standing at 25 ℃ for curing for 168 hours at room temperature, and thus obtaining the full-water polyurethane hard foam material.
Comparative example 1:
this comparative example differs from example 3 in that no polyester polyol is added.
The embodiment provides a full-water polyurethane rigid foam which comprises the following raw materials:
the component A comprises:
polyether polyol RF4110A 100g,
a foam stabilizer SD201 g,
0.1g of the amine catalyst A was added,
0.15g of the metal catalyst T12,
trimerization catalyst TMR 2g, water 4g.
The component B comprises: polyphenyl polymethylene isocyanate PM200 g.
The preparation method of the full-water polyurethane rigid foam comprises the following steps:
s1, accurately weighing the component A according to the weight in the formula, putting the component A into a cup, and stirring for 5min at a speed of 500r/min to obtain a first mixture;
s2, adding the isocyanate component B into the first mixture, and stirring for 12S at 1000r/min to obtain a second mixture;
and S3, pouring the second mixture into a mold for foaming, demolding after the foam is solidified, standing at 25 ℃ for curing for 168 hours at room temperature, and thus obtaining the full-water polyurethane hard foam material.
Comparative example 2:
this comparative example differs from example 3 in that the amount of trimerization catalyst TMR2 is reduced.
The embodiment provides a full-water polyurethane rigid foam which comprises the following raw materials:
the component A comprises:
polyether polyol RF4110A 70g,
30g of PES (polyester polyol) 504 g,
a foam stabilizer SD201 g,
0.1g of the amine-based catalyst A,
0.15g of the metal catalyst T12,
trimerization catalyst TMR 2g, water 4g.
The component B comprises:
polyphenyl polymethylene isocyanate PM200 g.
The preparation method of the all-water polyurethane rigid foam comprises the following steps:
s1, accurately weighing the component A according to the weight in the formula, putting the component A into a cup, and stirring for 5min at a speed of 500r/min to obtain a first mixture;
s2, adding the isocyanate component B into the first mixture, and stirring for 12S at 1000r/min to obtain a second mixture;
and S3, pouring the second mixture into a mold for foaming, demolding after the foam is solidified, standing at 25 ℃ for curing for 168 hours at room temperature, and obtaining the full-water polyurethane rigid foam material.
Comparative example 3:
this comparative example differs from example 3 in that the foam stabilizer SD201 was changed to a conventional siloxane 7705.
The embodiment provides a full water polyurethane rigid foam, which comprises the following raw materials:
the component A comprises:
polyether polyol RF4110A 70g,
30g of PES (polyester polyol) 504 g,
7705 g of siloxane foam homogenizing agent,
0.1g of the amine catalyst A was added,
0.15g of the metal catalyst T12,
trimerization catalyst TMR 2g, water 4g.
The component B comprises:
polyphenyl polymethylene isocyanate PM200 g.
The preparation method of the full-water polyurethane rigid foam comprises the following steps:
s1, accurately weighing the component A according to the weight in the formula, putting the component A into a cup, and stirring for 5min at a speed of 500r/min to obtain a first mixture;
s2, adding the isocyanate component B into the first mixture, and stirring for 12S at 1000r/min to obtain a second mixture;
and S3, pouring the second mixture into a mold for foaming, demolding after the foam is solidified, standing at 25 ℃ for curing for 168 hours at room temperature, and obtaining the full-water polyurethane rigid foam material.
The all-water polyurethane rigid foam materials obtained in the above examples and comparative examples were subjected to a cutting test, and the specific performance results thereof are shown in the following table 1:
TABLE 1
As can be seen from the above table, examples 1 to 3 have a rigid polyurethane foam density of not more than 70kg/m 3 Under the condition of (2), the compressive strength is still more than 0.7MPa, the compressive modulus is more than 20MPa, the cells are fine, and the pore size is about 150 mu m.
Therefore, the all-water polyurethane rigid foam material provided by the invention solves the problems of low strength and coarse and uneven foam holes of a low-density rigid foam product.
At present, the wind power foam core material polyurethane rigid foam material is only limited to high density: (A), (B), (C)>100kg·m -3 ) The compressive strength of the foam can reach more than 0.7 MPa.
The polyurethane rigid foam provided by the invention has low density and high compressive strength, can be applied to wind power foam core materials, and can also be applied to the aspects of supporting, filling and the like as structural materials.
The above description is only an example of the present invention, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention within the technical scope of the present invention.
Claims (3)
1. A full-water polyurethane rigid foam material comprises a component A and a component B, and is characterized in that the mass ratio of the component A to the component B is within the range of 100 to 160 to 240;
wherein, the component A comprises the following components in parts by weight:
60-90 parts of polyether polyol;
10-40 parts of polyester polyol;
2-6 parts of a foam stabilizer;
0.05-0.4 part of amine catalyst;
0.05-0.5 part of metal catalyst;
2-10 parts of a trimerization catalyst;
2-6 parts of a foaming agent;
wherein, the component B comprises the following components in parts by weight:
200-280 parts of isocyanate;
the functionality of the polyether polyol is 4-5, the hydroxyl value is 420-480mgKOH/g, the viscosity is 2000-4000mPa.s, and the water content is less than 0.1%;
the functionality of the polyester polyol is 5-7, the hydroxyl value is 380-420mgKOH/g, the viscosity is 2500-4000mPa.s, and the water content is less than 0.1%;
the foaming agent is water;
the polyether polyol is a product prepared based on the reaction of octafunctional sucrose with trifunctional glycerol as an initiator;
the polyester polyol is a product prepared by reacting tetrafunctional pyromellitic dianhydride with butanediol;
the foam stabilizer is polysiloxane-polyoxyalkylene ether block copolymer;
the amine catalyst is a high-activity gel catalyst, and the reaction rate constant is 1 x 10 -3 g·mol -1 ·min -1 The above;
the isocyanate is polyphenyl polymethylene isocyanate with NCO content of 30-32%;
the metal catalyst is an organic tin catalyst;
the trimerization catalyst is a trimerization catalyst TMR2 with a delayed action.
2. The method for preparing the all-water rigid polyurethane foam material as claimed in claim 1, wherein the method comprises the following steps:
s1, uniformly mixing polyether polyol, polyester polyol, a foam stabilizer, an amine catalyst, a metal catalyst, a trimerization catalyst and a foaming agent to obtain a first mixture;
s2, adding the isocyanate into the first mixture and uniformly mixing to obtain a second mixture;
s3, pouring the second mixture into a mold for foaming, demolding after the foam is solidified, and curing to obtain the all-water polyurethane rigid foam material;
the stirring speed in the step S1 is 200-3000r/min, and the stirring time is 5-10min;
the stirring speed in the step S2 is 200-3000r/min, and the stirring time is 10-15S;
the curing in the step S3 is to be placed for 4 to 7 days at room temperature or to be placed in an oven at the temperature of 90 ℃ for 4 to 7 hours.
3. The use of the rigid polyurethane foam material according to claim 1, wherein the rigid polyurethane foam material is used as a structural material for supporting and filling.
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