CN114133509B - High-density, high-strength and environment-friendly combined polyether and polyurethane material for LNG cushion block and preparation method thereof - Google Patents

High-density, high-strength and environment-friendly combined polyether and polyurethane material for LNG cushion block and preparation method thereof Download PDF

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CN114133509B
CN114133509B CN202111534856.3A CN202111534856A CN114133509B CN 114133509 B CN114133509 B CN 114133509B CN 202111534856 A CN202111534856 A CN 202111534856A CN 114133509 B CN114133509 B CN 114133509B
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polyether
polyether polyol
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cushion block
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CN114133509A (en
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王光辉
李学庆
李丽
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SHANGHAI DONGDA POLYURETHANE CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

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Abstract

The invention relates to the technical field of polyurethane, in particular to composite polyether for a high-density, high-strength and environment-friendly LNG cushion block, a polyurethane material and a preparation method thereof. The combined polyether comprises the following components in parts by mass: 45-55 parts of polyether polyol A, 20-30 parts of polyether polyol B, 20 parts of polyether polyol C, 5-10 parts of polyether polyol D, 1 part of foam stabilizer, 1.2-2.0 parts of catalyst, 10 parts of dimethyl carbonate, 0.3 part of water and 1.5-2.0 parts of cell opener. The combined polyether disclosed by the invention adopts an all-water system, is green and environment-friendly, ensures the strength of polyurethane foam, improves curing, improves demolding property and improves production efficiency; the prepared polyurethane material has high foam opening rate and high strength, improves the mold opening property and avoids cracking.

Description

High-density, high-strength and environment-friendly combined polyether and polyurethane material for LNG cushion block and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane, in particular to composite polyether for a high-density, high-strength and environment-friendly LNG cushion block, a polyurethane material and a preparation method thereof.
Background
The polyurethane foaming heat-insulating material is a heat-insulating material with the lowest heat conductivity coefficient and the best energy-saving effect in organic heat-insulating materials. The foaming agent used for the thermal insulation material has been developed and evolved for more than 40 years, and the foaming agent has been continuously improved in the aspects of energy conservation, environmental protection, energy consumption and the like from a first generation freon foaming agent (F-11), a second generation chlorofluorocarbon foaming agent (HCFC), a third generation Hydrofluorocarbon (HFC) foaming agent and a fourth generation hydrofluoroolefin foaming agent (HFO). However, the foaming agent belongs to a physical foaming agent, belongs to petrochemical derivatives and is derived from non-renewable resources, and the foaming agent can be gradually released in a natural environment along with foam aging in the thermal insulation material to cause damage to the environment.
At present, the green polyurethane taking water as the foaming agent has very wide application prospect. However, the heat-insulating materials have the defects of high viscosity, poor mold openness, easiness in cracking, high heat conductivity coefficient, easiness in shrinking and the like, and are not widely applied.
LNG develops rapidly recently, the national energy-saving and emission-reduction policies are met, in the construction process of LNG conveying pipelines, besides pipe shells, pipe brackets and other products, cushion blocks are required to be used in regions with uneven terrain, the polyurethane material is high in specific strength and can well support and pave, and the polyurethane material and polyurethane industry still applies a large amount of fluorine hydrocarbon or alkane physical foaming agents. There are great challenges in terms of both safety and environmental protection.
When the full water is used as the foaming agent, the full water system has the defects of high viscosity, poor mold opening property, easiness in cracking, low strength, high heat conductivity coefficient, easiness in shrinking and the like, and the high-density cushion block needs extremely high strength, and the cracking problem is more easily caused due to extremely high heat productivity when the high-density cushion block is prepared.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the high-density, high-strength and environment-friendly combined polyether for the LNG cushion block is provided, adopts an all-water system, is green and environment-friendly, solves the problems of low strength and die sinking cracking of the high-density cushion block prepared by the all-water system, ensures the strength of polyurethane foam, improves curing, improves demolding property and improves production efficiency; the invention also provides the polyurethane material, the foam opening rate is high, the strength is high, the mold opening performance is improved, and cracking is avoided; the invention also provides a preparation method of the composition.
The combined polyether for the high-density, high-strength and environment-friendly LNG cushion block comprises the following components in parts by weight:
Figure BDA0003412240220000011
Figure BDA0003412240220000021
the sum of the parts by mass of the polyether polyol A, the polyether polyol B, the polyether polyol C and the polyether polyol D is 100 parts.
Wherein, the hydroxyl value of the polyether polyol A is 440-470mgKOH/g, the viscosity at 25 ℃ is 13000-17000 mPa & s, and the water content is less than 0.2wt%; donol R6207, manufactured by Shanghai east chemical Limited company, is preferred.
The polyether polyol B has the functionality of 6, the hydroxyl value of 475-515mgKOH/g, the viscosity of 35000-45000 mPa & s at 25 ℃ and the water content of less than 0.2wt%; preferably Donol R6049, manufactured by shanghai great chemical limit company.
The hydroxyl value of the polyether polyol C is 330-350mgKOH/g, the viscosity at 25 ℃ is 230-370mPa & s, and the water content is less than 0.05wt%; preferred is polyether polyol Donol C305 available from Shanghai east chemical Limit.
The hydroxyl value of the polyether polyol D is 260-300mgKOH/g, the acid value is less than 0.1mgKOH/g, and the water content is less than 0.15%; preferred is polyether polyol Donol 204E from Shanghai east chemical Limit.
In some embodiments, the viscosity of the polyether polyol and the polyester polyol may each independently be a viscosity conventional in the art, such as a kinematic viscosity. The kinematic viscosity is generally measured using a rotational viscometer.
The foam stabilizer has a viscosity of 200 to 600 mPas at 25 ℃ and a water content of less than 0.3wt%; preferably, it is foam stabilizer S-198 supplied by Shanghai Maihao chemical technology, inc.
The viscosity of the pore former at 25 ℃ is 150-400 mPas, the specific gravity is 0.9-1.0g/ml, and the water content is less than 0.35wt%; NP-8 from Shanghai Xinjian Kogaku Co., ltd is preferable.
The catalyst is an amine catalyst or a delayed-type catalyst; preferably, the composite catalyst comprises N, N '-dimethylcyclohexylamine and Cat 220, wherein the mass ratio of the N, N' -dimethylcyclohexylamine to the Cat 220 is (0.2-0.5): (1.0-1.5).
The preparation method of the combined polyether for the high-density, high-strength and environment-friendly LNG cushion block is obtained by uniformly mixing all components of the combined polyether.
The polyurethane material for the high-density, high-strength and environment-friendly LNG cushion block is prepared by mixing the combined polyether and isocyanate according to the mass ratio of 1 (1-1.1).
The isocyanate is polymeric MDI with an NCO content of 30.5-32%, preferably PM 200 in Wanhua chemistry.
According to the preparation method of the polyurethane material for the high-density, high-strength and environment-friendly LNG cushion block, isocyanate and combined polyether in a predetermined weight proportion are uniformly mixed through a high-pressure machine, then the mixture is injected into a mold preheated to 30-35 ℃, and then the mold is cured and opened to obtain the polyurethane material for the LNG cushion block.
Compared with the prior art, the invention has the following beneficial effects:
(1) The combined polyether does not use a physical foaming agent, adopts a full-water system, and is green and environment-friendly;
(2) The polyether polyol with high functionality adopted by the combined polyether can ensure the strength of polyurethane foam, improve curing, improve demolding performance and improve production efficiency; part of Case polyether is adopted, so that the problem of cracking caused by too large stress after die opening is avoided;
(3) The polyether polyol, the catalyst and the like adopted by the combined polyether can effectively reduce reaction heat, and the use of part of the cell opening agent and pure EO chain segment polyether can improve the cell opening rate of foam, so that heat is released quickly, the die opening is improved, and cracking is avoided;
(4) The combined polyether disclosed by the invention uses dimethyl carbonate, so that the viscosity of a full water system can be reduced by taking the dimethyl carbonate as a diluent, the boiling point of the dimethyl carbonate is 90-91 ℃, the internal temperature of polyurethane foaming reaches over 140 ℃, and partial heat is taken away by gasification after the boiling point of the dimethyl carbonate is reached, so that the reaction heat is further reduced, the mold opening property is improved, and cracking is avoided.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization procedures used are synchronized with the filing date of the present disclosure. Where applicable, the contents of any patent, patent application or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent counterparts are incorporated by reference, especially as they disclose definitions relating to synthetic techniques, product and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided herein, the definition of that term provided herein controls.
The performance test criteria used in the examples are as follows:
(1) GB6343-1995: national standards for the determination of the apparent (bulk) density of foams and rubbers.
The present standard specifies the method of testing the apparent (bulk) density of foams and rubbers.
The standard is suitable for measuring the apparent total density and the apparent core density of the rigid foam plastic and the volume density of the semi-rigid and flexible foam plastic and the rubber.
(2) GB8813-2008: national standard for testing the compression strength of rigid foam.
The present standard specifies a method for measuring the compressive strength of a rigid foam, its relative deformation, and the compressive stress and the compressive modulus of elasticity at a relative deformation of 10%.
(3) GB8811-2008: national standard for the rigid foam dimensional stability test method.
The present standard specifies a method for determining the dimensional stability of rigid foams under specific conditions of temperature and relative humidity.
The standard is suitable for measuring the dimensional stability of the rigid foam.
(4) GB/T10799-2008: national standards for the determination of open and closed cell volume percentages of rigid foams.
This standard specifies the determination of the percent open and closed cell volume of the rigid foam.
The present criteria apply to foams containing cells divided by polymer membranes or cell walls into many small cells, which may be open (open) or closed (non-open) or a composite of these types.
The raw materials used in the examples were as follows:
polyether polyol Donol R6207, available from eastern chemical Limited, shanghai.
Polyether polyol Donol R6049, available from great chemists, shanghai, inc.
Polyether polyol Donol C305, available from great chemists, shanghai.
Polyether polyol Donol 204E, available from Shanghai east chemical Limited.
Foam stabilizer S-198, available from Shanghai Maihao chemical science and technology Co., ltd.
Cell opener NP-8 available from Shanghai Xinjian Kogyu Co., ltd.
Catalyst Cat 220 available from Shanghai Xin Sharpness Kogaku Co., ltd
Dimethyl carbonate, available from Shandong Shi Da Sheng Hua chemical group, inc.
Polymeric MDI PM 200, available from wanhua chemistry.
In a first aspect, the invention provides a combined polyether, which comprises the following components in parts by mass: 45-55 parts of Donol R6207, 20-30 parts of Donol R6049, 20 parts of Donol C305, 5-10 parts of Donol 204E, 1 part of S-198, 1.2-2.0 parts of catalyst, 10 parts of dimethyl carbonate and 1.5-2.0 parts of NP-8.
Wherein, the hydroxyl value of the Donol R6207 is 440-470mgKOH/g, the viscosity at 25 ℃ is 13000-17000 mPa & s, and the water content is less than 0.2wt%; donol R6049 with functionality of 6, hydroxyl value of 475-515mgKOH/g, viscosity of 35000-45000 mPa.s at 25 ℃, and water content less than 0.2wt%; donol C305 with hydroxyl value of 330-350mgKOH/g, viscosity of 230-370 mPa.s at 25 deg.C, and water content less than 0.05wt%; donol 204E, hydroxyl value of 260-300mgKOH/g, acid value less than 0.1mgKOH/g, water content less than 0.15%. The sum of the mass parts of the polyether polyols is 100 parts.
In order to improve the strength and the mold opening property of the LNG cushion block, the combined polyether disclosed by the invention does not use a physical foaming agent, adopts an all-water system, and is green and environment-friendly; the high-functionality polyether polyol can ensure the strength of polyurethane foam, improve curing, improve demolding property and improve production efficiency; part of Case polyether is adopted, so that the problem of cracking caused by too large stress after die opening is avoided; the adopted polyether polyol, catalyst and the like can effectively reduce the reaction heat, and the use of part of the cell opening agent and pure EO chain segment polyether can improve the foam opening rate, thereby releasing heat quickly, improving the die sinking and avoiding cracking; dimethyl carbonate is used as a diluent to reduce the viscosity of a full water system, the boiling point of the dimethyl carbonate is 90-91 ℃, the internal temperature of polyurethane foam reaches over 140 ℃, and partial heat is taken away by gasification after the boiling point of the dimethyl carbonate is reached, so that the reaction heat is further reduced, the mold opening property is improved, and cracking is avoided.
In a second aspect, the invention also provides a preparation method of the composite polyether, and the composite polyether is obtained by uniformly mixing the components.
In a third aspect, the invention provides a polyurethane material for an LNG cushion block, which is obtained by mixing the combined polyether and isocyanate according to the mass ratio of 1 (1-1.1).
The isocyanate is polymeric MDI having an NCO content of 30.5 to 32%, preferably PM 200 in Vawa chemistry.
The invention has high density, high strength and environmental protection
In a fourth aspect, the invention provides a preparation method of the polyurethane material for the LNG cushion block, wherein isocyanate and the composite polyether are uniformly mixed in a predetermined weight ratio through a high-pressure machine, and then are injected into a mold preheated to 30-35 ℃, and then are cured and opened to obtain the polyurethane material for the LNG cushion block.
The above preferred conditions may be combined arbitrarily to obtain preferred embodiments of the present invention without departing from the general knowledge in the art.
Examples 1 to 4 and comparative examples 1 to 4
The compositions of the starting materials of the conjugate polyethers of examples 1 to 4 and comparative examples 1 to 4 are shown in Table 1 in parts by mass.
TABLE 1 raw material compositions of examples 1-4 and comparative examples 1-4
Figure BDA0003412240220000051
Example 1:
a preparation method of a polyurethane material for a high-density, high-strength and environment-friendly LNG cushion block comprises the following steps:
(1) 45 parts of Donol R6207, 30 parts of Donol R6049, 20 parts of Donol C305, 5 parts of Donol 204E, 1 part of S-198, 0.2 part of N, N' -dimethylcyclohexylamine, 1.5 parts of Cat 220, 10 parts of dimethyl carbonate, 0.3 part of water and 1.5 parts of NP-8; adding the mixture into a stainless steel mixing kettle, stirring at the rotating speed of 500 rpm for 1 hour at room temperature, and discharging to obtain the high-density, high-strength and environment-friendly combined polyether for the LNG cushion block;
(2) The preparation method comprises the following steps of accurately metering and mixing materials by a high-pressure machine according to the mass ratio of 1.0 of the combined polyether for the high-density, high-strength and environment-friendly LNG cushion block to the isocyanate PM 200 at the temperature of 25 ℃, injecting the materials into a preheated (30-35 ℃) mold, curing for 24 hours, and opening the mold to obtain the LNG cushion block material.
Example 2
A preparation method of a polyurethane material for a high-density, high-strength and environment-friendly LNG cushion block comprises the following steps:
(1) 48 parts of Donol R6207, 26 parts of Donol R6049, 20 parts of Donol C305, 6 parts of Donol 204E, 1 part of S-198, 0.3 part of N, N' -dimethylcyclohexylamine, 1.3 parts of Cat 220, 10 parts of dimethyl carbonate, 0.3 part of water and 1.7 parts of NP-8; adding the mixture into a stainless steel mixing kettle, stirring at the rotation speed of 500 revolutions per minute for 1 hour at room temperature, and discharging to obtain the high-density, high-strength and environment-friendly combined polyether for the LNG cushion block;
(2) The preparation method comprises the following steps of accurately metering and mixing materials by a high-pressure machine according to the mass ratio of 1.05 of the combined polyether for the high-density, high-strength and environment-friendly LNG cushion block to the isocyanate PM 200 at the temperature of 25 ℃, injecting the materials into a preheated (30-35 ℃) mold, curing for 24 hours, and opening the mold to obtain the LNG cushion block material.
Example 3
A preparation method of a polyurethane material for a high-density, high-strength and environment-friendly LNG cushion block comprises the following steps:
(1) 50 parts of Donol R6207, 22 parts of Donol R6049, 20 parts of Donol C305, 8 parts of Donol 204E, 1 part of S-198, 0.4 part of N, N' -dimethylcyclohexylamine, 1.2 parts of Cat 220, 10 parts of dimethyl carbonate, 0.3 part of water and 1.8 parts of NP-8; adding the mixture into a stainless steel mixing kettle, stirring at the rotation speed of 500 revolutions per minute for 1 hour at room temperature, and discharging to obtain the high-density, high-strength and environment-friendly combined polyether for the LNG cushion block;
(2) Accurately metering and mixing the materials by a high-pressure machine according to the mass ratio of 1.1 of the combined polyether for the high-density, high-strength and environment-friendly LNG cushion block to the isocyanate PM 200 at the temperature of 25 ℃, injecting the materials into a preheated (30-35 ℃) mold, curing for 24 hours, and opening the mold to obtain the LNG cushion block.
Example 4
A preparation method of a polyurethane material for a high-density, high-strength and environment-friendly LNG cushion block comprises the following steps:
(1) 50 parts of Donol R6207, 20 parts of Donol R6049, 20 parts of Donol C305, 10 parts of Donol 204E, 1 part of S-198, 0.5 part of N, N' -dimethylcyclohexylamine, 1.0 part of Cat 220, 10 parts of dimethyl carbonate, 0.3 part of water and 2.0 parts of NP-8; adding the mixture into a stainless steel mixing kettle, stirring at the rotation speed of 500 revolutions per minute for 1 hour at room temperature, and discharging to obtain the high-density, high-strength and environment-friendly combined polyether for the LNG cushion block;
(2) Accurately metering and mixing the materials by a high-pressure machine according to the mass ratio of 1.1 of the combined polyether for the high-density, high-strength and environment-friendly LNG cushion block to the isocyanate PM 200 at the temperature of 25 ℃, injecting the materials into a preheated (30-35 ℃) mold, curing for 24 hours, and opening the mold to obtain the LNG cushion block.
Comparative example 1
A preparation method of a polyurethane material for an LNG cushion block comprises the following steps:
(1) 45 parts of Donol R6207, 30 parts of Donol R6049, 20 parts of Donol C305, 5 parts of Donol 204E, 1 part of S-198, 0.2 part of N, N' -dimethylcyclohexylamine, 1.5 parts of Cat 220, 0.3 part of water and 1.5 parts of NP-8; adding the mixture into a stainless steel mixing kettle, stirring at the rotating speed of 500 revolutions per minute for 1 hour at room temperature, and discharging to obtain the combined polyether for the LNG cushion block;
(2) And (2) accurately metering and mixing the materials by a high-pressure machine according to the mass ratio of 1.0 of the combined polyether for the LNG cushion block to the isocyanate PM 200 at the temperature of 25 ℃, injecting the materials into a preheated (30-35 ℃) mold, curing for 24 hours, opening the mold for cracking, curing for 36 hours, and opening the mold to obtain the product.
Comparative example 2
A preparation method of a polyurethane material for an LNG cushion block comprises the following steps:
(1) 54 parts of Donol R6207, 26 parts of Donol R6049, 20 parts of Donol C305, 1 part of S-198, 0.3 part of N, N' -dimethylcyclohexylamine, 1.3 parts of Cat 220, 10 parts of dimethyl carbonate and 0.3 part of water; adding the mixture into a stainless steel mixing kettle, stirring at the rotation speed of 500 revolutions per minute for 1 hour at room temperature, and discharging to obtain the combined polyether for the LNG cushion block;
(2) Accurately metering and mixing the materials by a high-pressure machine according to the mass ratio of 1.05 to 1.05 of the combined polyether for the LNG cushion block to the isocyanate PM 200 at the temperature of 25 ℃, injecting the materials into a preheated (30-35 ℃) mold, curing for 24 hours, opening the mold for cracking, curing for 30 hours, and opening the mold to obtain the product.
Comparative example 3
A preparation method of a polyurethane material for an LNG cushion block comprises the following steps:
(1) 60 parts of Donol R6207, 40 parts of Donol R6049, 1 part of S-198, 0.4 part of N, N' -dimethylcyclohexylamine, 1.2 parts of Cat 220, 10 parts of dimethyl carbonate, 0.3 part of water and 1.8 parts of NP-8; adding the mixture into a stainless steel mixing kettle, stirring at the rotating speed of 500 revolutions per minute for 1 hour at room temperature, and discharging to obtain the combined polyether for the LNG cushion block;
(2) Accurately metering and mixing the materials by a high-pressure machine according to the mass ratio of 1.1 of the combined polyether for the LNG cushion block to the isocyanate PM 200 at the temperature of 25 ℃, injecting the materials into a preheated (30-35 ℃) mold, curing for 24 hours, opening the mold for cracking, curing for 28 hours, and opening the mold to obtain the product.
Comparative example 4
A preparation method of a polyurethane material for an LNG cushion block comprises the following steps:
(1) 100 parts of 4110, 1 part of S-198, 0.5 part of N, N' -dimethylcyclohexylamine, 1.0 part of Cat 220 and 0.3 part of water; adding the mixture into a stainless steel mixing kettle, stirring at the rotating speed of 500 revolutions per minute for 1 hour at room temperature, and discharging to obtain the combined polyether for the LNG cushion block;
(2) Accurately metering and mixing the materials by a high-pressure machine according to the mass ratio of 1.1 of the combined polyether for the LNG cushion block to the isocyanate PM 200 at the temperature of 25 ℃, injecting the materials into a preheated (30-35 ℃) mold, curing for 24 hours, opening the mold for cracking, curing for 48 hours, and opening the mold to obtain the product.
The polyurethane materials prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to the effect test, and the test results are shown in table 2 below.
Table 2 polyurethane material property data
Figure BDA0003412240220000081
As can be seen from Table 2, the aperture ratio of the polyurethane material for the LNG cushion block prepared by the invention is obviously improved, the reaction heat is obviously reduced, the mold opening property is obviously improved, the production efficiency is greatly improved, the foam compression strength reaches more than 21mPa, and the use requirement of the LNG pipeline cushion block can be met.

Claims (5)

1. The utility model provides a high density, high strength, environment-friendly polyether block for LNG cushion which characterized in that: the composition comprises the following components in parts by mass:
45-55 parts of polyether glycol A,
20-30 parts of polyether polyol B,
20 parts of polyether glycol C, 20 parts of polyether glycol,
5-10 parts of polyether polyol D,
1 part of a foam stabilizer, namely 1 part,
1.2 to 2.0 portions of catalyst,
10 parts of dimethyl carbonate, namely 10 parts of dimethyl carbonate,
0.3 part of water, namely,
1.5-2.0 parts of a pore forming agent;
the sum of the mass parts of the polyether polyol A, the polyether polyol B, the polyether polyol C and the polyether polyol D is 100 parts;
wherein, the polyether polyol A is Donol R6207, the polyether polyol B is Donol R6049, the polyether polyol C is Donol C305, and the polyether polyol D is Donol 204E;
the foam stabilizer is S-198, the viscosity at 25 ℃ is 200-600 mPa.s, and the water content is less than 0.3wt%;
the pore former is NP-8, the viscosity at 25 ℃ is 150-400 mPa.s, the specific gravity is 0.9-1.0g/ml, and the water content is less than 0.35wt%;
the catalyst is a composite catalyst comprising N, N '-dimethylcyclohexylamine and Cat 220, and the mass ratio of the N, N' -dimethylcyclohexylamine to the Cat 220 is (0.2-0.5): (1.0-1.5).
2. The preparation method of the composite polyether for the high-density, high-strength and environment-friendly LNG cushion block as claimed in claim 1, wherein the preparation method comprises the following steps: and uniformly mixing all the components of the combined polyether to obtain the polyether.
3. The utility model provides a high density, high strength, environment-friendly insulation material for LNG cushion which characterized in that: obtained by mixing the combined polyether and isocyanate according to the mass ratio of 1 (1-1.1).
4. The ultra-high density, high strength, environmentally friendly insulation material for LNG bolsters of claim 3, wherein: the isocyanate is polymeric MDI having an NCO content of 30.5-32%.
5. The method for preparing the thermal insulation material for the high-density, high-strength and environment-friendly LNG cushion block as claimed in claim 4, wherein the method comprises the following steps: uniformly mixing isocyanate and combined polyether in a predetermined weight ratio by a high pressure machine, injecting the mixture into a mold preheated to 30-35 ℃, curing, and opening the mold to obtain the polyurethane material for the LNG cushion block.
CN202111534856.3A 2021-12-15 2021-12-15 High-density, high-strength and environment-friendly combined polyether and polyurethane material for LNG cushion block and preparation method thereof Active CN114133509B (en)

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JP2007002118A (en) * 2005-06-24 2007-01-11 Nichias Corp Polyisocyanate component and rigid polyurethane foam
CN104788642A (en) * 2015-05-11 2015-07-22 南京林业大学 Hard polyurethane foam for ultralow-temperature insulation and preparation method thereof
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