CN116444751B - All-water spraying winding polyol composite material, polyurethane rigid foam plastic and preparation method of polyurethane rigid foam plastic heat-insulation pipeline - Google Patents

All-water spraying winding polyol composite material, polyurethane rigid foam plastic and preparation method of polyurethane rigid foam plastic heat-insulation pipeline Download PDF

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CN116444751B
CN116444751B CN202210008096.0A CN202210008096A CN116444751B CN 116444751 B CN116444751 B CN 116444751B CN 202210008096 A CN202210008096 A CN 202210008096A CN 116444751 B CN116444751 B CN 116444751B
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polyol
polyurethane
foam
composite material
foam plastic
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CN116444751A (en
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彭宏伟
朱霞林
冷柏逊
陈静
吕嘉乐
沈显尧
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Wanhua Chemical Ningbo Rongwei Polyurethane Co Ltd
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Wanhua Chemical Ningbo Rongwei 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • 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
    • C08G18/4825—Polyethers containing two 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
    • C08G18/28—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
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
    • 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
    • C08G2110/0025—Foam properties rigid
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses an all-water spraying winding polyol composite material which comprises polyether polyol, polyester polyol, a foaming agent, a catalyst, a foam stabilizer and a viscosity reducer. Also discloses a polyurethane rigid foam plastic of an all-water system, which is applied to the continuous spraying winding method for producing polyurethane heat-insulation pipes. The polyurethane hard foam plastic is prepared by mixing a polyol combination material and isocyanate according to the following ratio of 1:1.3 to 1.5 mass ratio. The polyurethane heat-insulating pipeline produced by the continuous spraying winding method is better in foam mechanical property, environment-friendly and pollution-free, and can save production cost and improve production efficiency.

Description

All-water spraying winding polyol composite material, polyurethane rigid foam plastic and preparation method of polyurethane rigid foam plastic heat-insulation pipeline
Technical Field
The invention relates to a polyurethane hard foam composite material and polyurethane hard foam plastic applied to a continuous spraying winding process for producing a heat-insulating pipeline and a preparation method of the polyurethane hard foam plastic heat-insulating pipeline, and belongs to the field of production of polyurethane hard foam heat-insulating pipes.
Background
The heat-insulating pipeline has good heat-insulating effect, is mainly applied to the process of conveying various cold and hot media, comprises industries such as central heating, municipal administration, chemical industry, petroleum and the like, and can effectively save a large amount of energy. The polyurethane hard foam has excellent heat preservation and insulation performance, long service life and low water absorption, can effectively cope with various complex and humid environments, is an ideal heat preservation and insulation material, and is widely applied to the production process of various heat preservation pipelines.
The traditional production method of the polyurethane heat-insulating pipeline is a pouring process, the process is intermittent, the production efficiency is low, and the filling density of polyurethane is high. With the innovation of the process, the continuous spraying winding process for producing the polyurethane heat-insulation pipeline is gradually popularized in China in recent two years, and the production efficiency of the polyurethane heat-insulation pipeline is greatly improved.
At present, HCFC-141b is still the main foaming agent of the spraying winding composite material of the heat preservation pipeline, and HCFC-141b and HFC-245fa are transitional physical foaming agents, so that the traditional chlorofluorocarbon foaming agents can damage an ozone layer, and the foaming agents can further accelerate the elimination speed under the condition of increasing global environmental pressure. Among them, alkane foaming agents such as cyclopentane are an ideal alternative, and are widely used in the field of polyurethane rigid foam. However, cyclopentane is a dangerous chemical, is volatile, flammable and explosive, and for a continuous spray winding process, the combination material generates strong atomization when being sprayed, so that the danger coefficient during use is also greatly increased. The all-water foaming technique is also a very desirable foaming scheme, water as a chemical blowing agent being foamed by reaction with isocyanate to form carbon dioxide gas. However, in all-water foaming compositions, the viscosity tends to be higher due to the reduced foaming dose; furthermore, for the spray winding process, the reaction is very rapid and heat builds up. Meanwhile, the reaction of water and isocyanate is a severe exothermic reaction, so that heat accumulation is further promoted, foam core burning is easy to cause, and the foam curing speed is delayed; when the continuous spraying winding process is used for production, the foam needs to be rolled by a tire, and if the toughness and the internal strength of the foam are insufficient, the foam is easy to bulge, crack, fall off and the like after bearing pressure. Therefore, there is a need to explore a more effective solution to meet the demanding requirements of continuous spray winding processes.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the all-water spraying winding polyol composite material, which effectively improves the applicability and the operation latitude of the all-water polyurethane rigid foam plastic in the spraying winding process.
Meanwhile, the invention also provides a preparation method of the polyurethane rigid foam plastic and the polyurethane rigid foam plastic heat-insulation pipeline,
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The all-water spray winding polyol composite material is characterized by comprising polyether polyol, polyester polyol, a foaming agent, a catalyst, a foam stabilizer and a viscosity reducer; the polyester polyol is 3-phenyl glutaric acid polyester polyol.
The 3-phenyl glutaric acid polyester polyol has a structure shown in a formula I:
Wherein n is an integer of 2 to 8.
Further, the hydroxyl value of the 3-phenyl glutaric acid polyester polyol is 200-380mgKOH/g, and the viscosity is 7000-15000 mPa.s (25 ℃).
A preparation method of 3-phenyl glutaric acid polyester polyol shown in formula I comprises the following steps:
3-phenyl glutaric acid, ethylene glycol, antioxidant and catalyst are used as raw materials, and the 3-phenyl glutaric acid polyester polyol is prepared through esterification reaction, wherein the reaction formula is as follows:
The antioxidant is one or more selected from IRGANOX1098, IRGANOX1035, IRGANOX245, IRGANOX1135, IRGANOX1010 and IRGANOX 1520. IRGANOX1010 is preferred.
The catalyst is any one or more of stannous chloride, stannic acetate, stannous octoate, tetrabutyl titanate or tetraisopropyl titanate. Tetrabutyl titanate is preferred.
As a preferred embodiment, the 3-phenyl glutaric acid polyester polyol comprises the following preparation steps:
3-phenyl glutaric acid and ethylene glycol are mixed according to a mole ratio of 1: 1.0-2.0, then adding a catalyst and an antioxidant, wherein the addition amount of the catalyst is 0.4-1.0% of the total weight of 3-phenyl glutaric acid and ethylene glycol, the addition amount of the antioxidant is 0.05-0.4% of the total weight of 3-phenyl glutaric acid and ethylene glycol, heating to 130-180 ℃, starting stirring and reacting at constant temperature for 1-3h, then heating to 200-250 ℃ at the speed of 3-5 ℃/min, continuing to react for 2-4h, when the acid value is less than or equal to 30mgKOH/g, starting vacuumizing and dehydrating, when the acid value is less than or equal to 5mgKOH/g, cooling to 100-140 ℃, and then filtering and packaging.
The 3-phenyl glutaric acid polyester polyol is introduced into polyether polyol, can generate synergistic effect with polyether polyol, has high polarity and high cohesive strength while taking all aspects of performances into consideration, can effectively improve the rigidity of a soft segment part in a polyurethane macromolecular chain, enhances the external force resistance of the molecular chain, can effectively improve the strength of polyurethane foam and improves the pressure-bearing performance of the foam.
As a preferred embodiment, an all-water spray-wound polyol composition is a mixture comprising the following components in mass percent:
In the invention, the foaming agent does not contain any physical foaming agent, and the foaming agent is all environment-friendly pollution-free chemical foaming agent-water.
In the invention, the viscosity reducer is dimethyl carbonate, the viscosity is 0.625 mPa.s (25 ℃), and the boiling point is 90.1 ℃.
The invention relates to an all-water composition containing 3-phenyl glutaric acid polyester polyol and dimethyl carbonate. The spraying winding process has high requirements on the pressure-bearing performance of the polyurethane foam, and the 3-phenyl glutaric acid polyester polyol with benzene ring has high polarity and high cohesive strength, so that the rigidity of a soft segment part in a polyurethane macromolecular chain can be effectively enhanced, the external force resistance of the molecular chain is enhanced, and the strength of the polyurethane foam can be effectively improved; in the whole water spraying process, the problem of heat accumulation easily occurs, so that the phenomenon of burning and pinholes of foam occurs; the introduction of the dimethyl carbonate can not only reduce the viscosity of the polyol composite material and enhance the toughness of polyurethane foam, but also improve the heat accumulation problem in the process of full water spraying, and the dimethyl carbonate has a narrow boiling point range, higher evaporation temperature and higher evaporation speed, so that the volatilization of the dimethyl carbonate can play a certain role in heat buffering in the process of full water spraying. The invention effectively improves the applicability and operation latitude of the all-water polyurethane rigid foam plastic in the spraying winding process through the use of the novel polyester polyol and the adjustment of the formula.
In the invention, the polyether polyol A is sucrose polyether polyol, the hydroxyl value is 300-450mgKOH/g, and the viscosity is 8000-14000 mPa.s (25 ℃).
In the invention, the polyether polyol B is sorbitol polyether polyol, the hydroxyl value is 380-480 mgKOH/g, and the viscosity is 20000-35000 mPa.s (25 ℃).
In the invention, the polyether polyol C is propylene glycol polyether polyol, the hydroxyl value is 60-150 mgKOH/g, and the viscosity is 50-200 mPa.s (25 ℃).
In the present invention, the polyester polyol D is the above-mentioned 3-phenylpentanedioic acid polyester polyol, and has a hydroxyl value of 200 to 380mgKOH/g and a viscosity of 7000 to 15000 mPas (25 ℃ C.).
In the present invention, the foam stabilizer is one or more of B84806, LK221, dongdra H3636, DC193, B8404 and AK 8812.
In the invention, the catalyst is one or more of pentamethyl diethylenetriamine, N-dimethyl cyclohexylamine, triethylene diamine, 1, 4-dimethyl piperazine, potassium isooctanoate, dibutyl tin dilaurate, quaternary ammonium formate and potassium acetate.
In the invention, the preparation steps of the composite material are as follows:
According to a certain formula proportion, polyether polyol A, polyether polyol B, polyether polyol C and polyester polyol D are added into a stirring kettle, the temperature is controlled at 75-80 ℃, then a foam stabilizer, a catalyst, a viscosity reducer and water are added into the stirring kettle, the stirring speed is 80 revolutions per minute, stirring is carried out for 40-50 minutes, and indexes such as moisture, viscosity, reaction time and density are detected to be qualified.
Polyurethane rigid foam plastic applied to pipeline heat preservation: the foam plastic is prepared by mixing and foaming isocyanate and polyol combination materials, wherein the mixing mass ratio of the isocyanate to the polyol combination materials is 1.3-1.5: 1.
The isocyanate is polymethylene polyphenyl polyisocyanate, preferably polymethylene polyphenyl polyisocyanate PM200 with a functionality of 2.6-2.7 produced by Wanhua chemical group Co., ltd.
The polyol combination material is the combination material.
And mixing PM200 with the polyol composite material in a polyurethane spraying machine, uniformly spraying the mixture on a steel pipe which is rotating at a constant speed, foaming, curing, forming and winding with PE, and finally preparing the polyurethane heat-insulation pipeline.
The density of the polyurethane foam prepared by the invention is more than or equal to 60kg/m 3; the closing rate is more than or equal to 90 percent; the heat conductivity coefficient is less than or equal to 0.033W/mK; the radial compression strength is more than or equal to 0.3Mpa; the average size of the cells is less than or equal to 0.5mm; the water absorption rate is less than or equal to 8 percent; when the outer protective layer of the heat-insulating layer operates, the surface temperature of the outer protective tube is less than or equal to 50 ℃.
A preparation method of a polyurethane hard foam plastic heat-insulation pipeline comprises the following steps:
(1) Uniformly mixing polyether polyol, a foaming agent, a catalyst, a foam stabilizer and a viscosity reducer according to a certain proportion to prepare a polyol composite material;
(2) Mixing the polyol combination material prepared in the step (1) with isocyanate according to a certain proportion by a high-pressure spraying machine, uniformly spraying the mixture on a steel pipe which is rotating at a constant speed, and preparing the final polyurethane hard foam plastic heat-insulation pipeline through curing molding and PE winding.
The beneficial effects of the invention are as follows:
(1) The polyurethane hard foam composite material is an all-water system, does not contain any physical foaming agent, has zero Ozone Destruction Potential (ODP) and extremely low Global Warming Potential (GWP), and is environment-friendly and pollution-free.
(2) The polyurethane hard foam composite material is added with the small-molecule dimethyl carbonate, can be used as a viscosity reducer to effectively reduce the viscosity of the composite material, and effectively inhibit the escape of carbon dioxide in the foam holes of the polyurethane heat-insulating pipe at high temperature, so that the foam stability is better, and the toughness is better.
(3) The polyurethane hard foam composite material is added with small molecular dimethyl carbonate. The dimethyl carbonate has higher evaporation temperature and higher evaporation speed, and in the foaming process, the vaporization of the dimethyl carbonate can effectively buffer the heat in the whole water foaming process, so that the heat is prevented from rising sharply, and the burning is avoided.
(4) The polyurethane hard foam composition of the invention is added with 3-phenyl glutaric acid polyester polyol. The 3-phenyl glutaric acid polyester polyol contains benzene ring and ester group, has high cohesive strength, can play a synergistic effect with polyether polyol, effectively improves the strength of polyurethane foam, and improves the pressure-bearing performance of the foam in the spray winding process.
Detailed Description
The invention is further described in detail below in connection with specific embodiments:
The raw materials used in the examples include:
The polyether polyol A is sucrose polyether polyol R2839 produced by Wanhua chemical (Ningbo) Rong Wei polyurethane limited company, the hydroxyl value is 400-420 mgKOH/g, and the viscosity is 9000-10000 mPa.s.
The polyether polyol B is sorbitol polyether polyol R6245 produced by Wanhua chemical (Ningbo) Rong Wei polyurethane limited company, the hydroxyl value is 440-460 mgKOH/g, and the viscosity is 28000-31000 mPa.s.
The polyether polyol C is propylene glycol polyether polyol C2010 produced by Wanhua chemical (Ningbo) Rong Wei polyurethane limited company, the hydroxyl value is 100-110 mgKOH/g, and the viscosity is 150-200 mPa.s.
The polyester polyol D is 3-phenyl glutaric acid polyester polyol and is self-made.
The foam stabilizer is B84806, which is a company of Yingchangshan solid (China) investment Co.
The viscosity reducer is dimethyl carbonate.
The catalyst is pentamethyl diethylenetriamine, N-dimethyl cyclohexylamine, triethylene diamine and potassium acetate.
The foaming agent is water.
Example 1
Preparation of 3-phenyl glutaric acid polyester polyol:
(1) 3-phenyl glutaric acid and ethylene glycol are mixed according to a mol ratio of 1:1.4, heating to 80 ℃ in proportion, and uniformly mixing;
(2) Adding tetrabutyl titanate accounting for 0.6 percent of the total weight of the 3-phenyl glutaric acid and the ethylene glycol and IRGANOX1010 (Basf (China) Co., ltd.) accounting for 0.1 percent of the total weight of the 3-phenyl glutaric acid and the ethylene glycol into the system, heating to 130 ℃, stirring and reacting for 2 hours at constant temperature;
(3) Heating to 200 ℃ at the speed of 3-5 ℃/min, continuing to react for 2h, when the acid value is less than or equal to 30mgKOH/g, starting vacuumizing and dehydrating, when the transesterification reaction is carried out until the acid value is less than or equal to 5mgKOH/g, cooling to 100 ℃, and then filtering and packaging;
(4) The 3-phenylglutarate polyester polyol was obtained, and had a hydroxyl value of 280mgKOH/g and a viscosity of 15000 mPa.s.
Example 2
(1) Preparing a polyol composition:
the polyol composite material comprises the following components in percentage by mass:
The preparation process of the polyol composition comprises the following steps: adding polyether polyol R2839, R6245, C2010 and 3-phenyl glutaric acid polyester polyol into a stirring kettle, stirring and controlling the temperature to 80 ℃, adding dimethyl carbonate, B84806, pentamethyl diethylenetriamine, N-dimethyl cyclohexylamine, potassium acetate and water, stirring at the speed of 80R/min for 40min, stirring uniformly, and cooling to room temperature to obtain the polyol composite material.
(2) Preparation of polyurethane rigid foam:
Parameters of a polyurethane high-pressure spraying machine are adjusted, polymethylene polyphenyl polyisocyanate PM200 and a polyol composite material are uniformly sprayed on a steel pipe which is rotating and advancing at a uniform speed through the high-pressure spraying machine according to the mass ratio of 1.5:1, the material temperature is 42-45 ℃, the pressure is 100-130bar, the flow is 150g/s, and polyurethane foam is automatically solidified and formed on the steel pipe.
The properties of the polyurethane foam obtained in the above manner are shown in the following table:
Physical Properties Unit (B) Test results Technical index Test standard
Density of kg/m3 78 ≥60 GB/T6343
Radial compressive Strength Mpa 0.593 ≥0.3 GB/T8813
Water absorption rate ％ 3.61 ≤8％ GB/T29046
Closed pore rate ％ 94 ≥90％ GB/T10799
Coefficient of thermal conductivity at 50 DEG C W/(m.k) 0.0313 ≤0.033 GB/T10294
Average cell size mm 0.20 ≤0.5mm GB/T12811
High temperature dimensional stability ％ 0.9 ≤1.5％ GBT 8811
Example 3
(1) Preparing a polyol composition:
The polyol composite material comprises the following components in percentage by mass:
The preparation process of the polyol composition comprises the following steps: adding polyether polyol R2839, R6245, C2010 and 3-phenyl glutaric acid polyester polyol into a stirring kettle, stirring and controlling the temperature to 80 ℃, adding dimethyl carbonate, B84806, pentamethyl diethylenetriamine, N-dimethyl cyclohexylamine, potassium acetate and water, stirring at the speed of 80R/min for 40min, stirring uniformly, and cooling to room temperature to obtain the polyol composite material.
(2) Preparation of polyurethane hard foam composition:
Parameters of a polyurethane high-pressure spraying machine are adjusted, polymethylene polyphenyl polyisocyanate PM200 and a polyol composite material are uniformly sprayed on a steel pipe which is rotating and advancing at a uniform speed through the high-pressure spraying machine according to the mass ratio of 1.5:1, the material temperature is 42-45 ℃, the pressure is 100-130bar, the flow is 150g/s, and polyurethane foam is automatically solidified and formed on the steel pipe.
The properties of the polyurethane foam obtained in the above manner are shown in the following table:
Physical Properties Unit (B) Test results Technical index Test standard
Density of kg/m3 70 ≥60 GB/T6343
Radial compressive Strength Mpa 0.553 ≥0.3 GB/T8813
Water absorption rate ％ 3.45 ≤8％ GB/T29046
Closed pore rate ％ 93 ≥90％ GB/T10799
Coefficient of thermal conductivity at 50 DEG C W/(m.k) 0.0305 ≤0.033 GB/T10294
Average cell size mm 0.20 ≤0.5mm GB/T12811
High temperature dimensional stability ％ 1.0 ≤1.5％ GBT 8811
Example 4
(1) Preparing a polyol composition:
The polyol composite material comprises the following components in percentage by mass:
Composition of the components Mass fraction (wt%)
R2839 21.5
R6245 25
C2010 25
3-Phenyl glutaric acid polyester polyol 10
Dimethyl carbonate 8
B84806 2
Pentamethyldiethylenetriamine 1.5
Triethylene diamine 1.5
Potassium acetate 1.5
Water and its preparation method 4
The preparation process of the polyol composition comprises the following steps: adding polyether polyol R2839, R6245, C2010 and 3-phenyl glutaric acid polyester polyol into a stirring kettle, stirring while controlling the temperature to 80 ℃, adding dimethyl carbonate, B84806, pentamethyl diethylenetriamine, triethylenediamine, potassium acetate and water, stirring at the speed of 80 revolutions per minute for 40 minutes, stirring uniformly, and cooling to room temperature to obtain the polyol composite material.
(2) Preparation of polyurethane hard foam composition:
Parameters of a polyurethane high-pressure spraying machine are adjusted, polymethylene polyphenyl polyisocyanate PM200 and a polyol composite material are uniformly sprayed on a steel pipe which is rotating and advancing at a uniform speed through the high-pressure spraying machine according to the mass ratio of 1.5:1, the material temperature is 42-45 ℃, the pressure is 100-130bar, the flow is 150g/s, and polyurethane foam is automatically solidified and formed on the steel pipe.
The properties of the polyurethane foam obtained in the above manner are shown in the following table:
Physical Properties Unit (B) Test results Technical index Test standard
Density of kg/m3 63 ≥60 GB/T6343
Radial compressive Strength Mpa 0.461 ≥0.3 GB/T8813
Water absorption rate ％ 3.40 ≤8％ GB/T29046
Closed pore rate ％ 94 ≥90％ GB/T10799
Coefficient of thermal conductivity at 50 DEG C W/(m.k) 0.0296 ≤0.033 GB/T10294
Average cell size mm 0.20 ≤0.5mm GB/T12811
High temperature dimensional stability ％ 1.3 ≤1.5％ GBT 8811
Comparative example 1
(1) Preparing a polyol composition:
The polyol composite material comprises the following components in percentage by mass:
Composition of the components Mass fraction (wt%)
R2839 29
R6245 30
C2010 30
B84806 2
Pentamethyldiethylenetriamine 1.5
N, N-dimethylcyclohexylamine 2
Potassium acetate 1.5
Water and its preparation method 4
The preparation process of the polyol composition comprises the following steps: adding polyether polyols R2839, R6245 and C2010 into a stirring kettle, stirring while controlling the temperature to 80 ℃, adding B84806, pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, potassium acetate and water, stirring at a rotation speed of 80 revolutions per minute for 40 minutes, and cooling to room temperature after stirring uniformly to obtain a polyol composite material.
(2) Preparation of polyurethane hard foam composition:
Parameters of a polyurethane high-pressure spraying machine are adjusted, polymethylene polyphenyl polyisocyanate PM200 and a polyol composite material are uniformly sprayed on a steel pipe which is rotating and advancing at a uniform speed through the high-pressure spraying machine according to the mass ratio of 1.5:1, the material temperature is 42-45 ℃, the pressure is 100-130bar, the flow is 150g/s, and polyurethane foam is automatically solidified and formed on the steel pipe.
The properties of the polyurethane foam obtained in the above manner are shown in the following table:
Physical Properties Unit (B) Test results Technical index Test standard
Density of kg/m3 65 ≥60 GB/T6343
Radial compressive Strength Mpa 0.362 ≥0.3 GB/T8813
Water absorption rate ％ 10.4 ≤8％ GB/T29046
Closed pore rate ％ 85 ≥90％ GB/T10799
Coefficient of thermal conductivity at 50 DEG C W/(m.k) 0.0293 ≤0.033 GB/T10294
Average cell size mm 0.20 ≤0.5mm GB/T12811
High temperature dimensional stability ％ 2.3 ≤1.5％ GBT 8811
Comparative example 2
(1) Preparing a polyol composition:
The polyol composite material comprises the following components in percentage by mass:
Composition of the components Mass fraction (wt%)
R2839 32
R6245 30
C2010 20
Dimethyl carbonate 8
B84806 2
Pentamethyldiethylenetriamine 1.5
N, N-dimethylcyclohexylamine 2
Potassium acetate 1.5
Water and its preparation method 3
The preparation process of the polyol composition comprises the following steps: adding polyether polyols R2839, R6245 and C2010 into a stirring kettle, stirring while controlling the temperature to 80 ℃, adding dimethyl carbonate, B84806, pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, potassium acetate and water, stirring at a speed of 80 revolutions per minute for 40 minutes, and cooling to room temperature after stirring uniformly to obtain a polyol composite material.
(2) Preparation of polyurethane hard foam composition:
Parameters of a polyurethane high-pressure spraying machine are adjusted, polymethylene polyphenyl polyisocyanate PM200 and a polyol composite material are uniformly sprayed on a steel pipe which is rotating and advancing at a uniform speed through the high-pressure spraying machine according to the mass ratio of 1.5:1, the material temperature is 42-45 ℃, the pressure is 100-130bar, the flow is 150g/s, and polyurethane foam is automatically solidified and formed on the steel pipe.
The properties of the polyurethane foam obtained in the above manner are shown in the following table:
Physical Properties Unit (B) Test results Technical index Test standard
Density of kg/m3 75 ≥60 GB/T6343
Radial compressive Strength Mpa 0.481 ≥0.3 GB/T8813
Water absorption rate ％ 3.85 ≤8％ GB/T29046
Closed pore rate ％ 93 ≥90％ GB/T10799
Coefficient of thermal conductivity at 50 DEG C W/(m.k) 0.0307 ≤0.033 GB/T10294
Average cell size mm 0.20 ≤0.5mm GB/T12811
High temperature dimensional stability ％ 1.4 ≤1.5％ GBT 8811

Claims (11)

1. An all-water spray-wrapped polyol composition comprising 15 to 35wt% sucrose polyether polyol, 15 to 30wt% sorbitol polyether polyol, 10 to 25wt% propylene glycol polyether polyol, 10 to 20wt% 3-phenyl glutaric acid polyester polyol, 3 to 4wt% water, 3 to 7wt% catalyst, 1 to 3wt% foam stabilizer and 3 to 8wt% dimethyl carbonate, based on the total amount of the composition;
Wherein the sucrose polyether polyol has a hydroxyl value of 300-450mgKOH/g and a viscosity of 8000-14000 mPa.s at 25 ℃; sorbitol polyether polyol with hydroxyl value of 380-480mgKOH/g and viscosity of 20000-35000 mPa.s at 25 ℃; propylene glycol polyether polyol having a hydroxyl value of 60 to 150mgKOH/g and a viscosity of 50 to 200 mPa.s at 25 ℃;
the 3-phenyl glutaric acid polyester polyol has a structure shown in a formula I:
Wherein n is an integer of 2 to 8; the hydroxyl value is 200-380mgKOH/g, and the viscosity at 25 ℃ is 7000-15000 mPas.
2. The combination according to claim 1, wherein: the foam stabilizer is selected from one or more of B84806, LK221, dongdi H3636, DC193, B8404, AK 8812.
3. The composition of claim 2, wherein the foam stabilizer is B84806.
4. The combination according to claim 1, wherein: the catalyst is selected from one or more of pentamethyl diethylenetriamine, N-dimethyl cyclohexylamine, triethylene diamine, 1, 4-dimethyl piperazine, potassium isooctanoate, dibutyl tin dilaurate, quaternary ammonium formate and potassium acetate.
5. The composite material according to claim 1, wherein the 3-phenyl glutaric acid polyester polyol is prepared by using 3-phenyl glutaric acid, ethylene glycol, an antioxidant and a catalyst as raw materials through esterification reaction.
6. The composition of claim 5, wherein the antioxidant is IRGANOX1010.
7. The composition of claim 5, wherein the catalyst used in the preparation of the 3-phenyl glutarate polyester polyol is tetrabutyl titanate.
8. The polyurethane rigid foam plastic for pipeline heat preservation is characterized by being formed by mixing and foaming a polyol combination material and isocyanate, wherein the polyol combination material is the all-water spraying winding polyol combination material according to any one of claims 1-7.
9. The rigid polyurethane foam according to claim 8, wherein the mass ratio of the polyol combination to the isocyanate is 1:1.3 to 1.5.
10. The rigid polyurethane foam according to claim 8 or 9, wherein the density of the rigid polyurethane foam is not less than 60kg/m 3; the closing rate is more than or equal to 90 percent; the heat conductivity coefficient is less than or equal to 0.033W/mK; the radial compression strength is more than or equal to 0.3Mpa; the average size of the cells is less than or equal to 0.5mm; the water absorption rate is less than or equal to 8 percent; when the outer protective layer of the heat-insulating layer operates, the surface temperature of the outer protective tube is less than or equal to 50 ℃.
11. A method for preparing a polyurethane rigid foam insulation pipe from a composite according to any one of claims 1 to 7 or a polyurethane rigid foam according to any one of claims 8 to 10, comprising the steps of:
(1) Uniformly mixing polyether polyol, polyester polyol, a foaming agent, a catalyst, a foam stabilizer and a viscosity reducer according to a certain proportion to prepare a polyol composite material;
(2) Mixing the polyol combination material prepared in the step (1) with isocyanate according to a certain proportion by a high-pressure spraying machine, uniformly spraying the mixture on a steel pipe which is rotating at a constant speed, and preparing the final polyurethane hard foam plastic heat-insulation pipeline through curing molding and PE winding.
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