CN111234677B - Environment-friendly rigid polyurethane spraying material for polyethylene-wound prefabricated direct-buried thermal insulation pipe and preparation method thereof - Google Patents
Environment-friendly rigid polyurethane spraying material for polyethylene-wound prefabricated direct-buried thermal insulation pipe and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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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
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
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- 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
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- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- 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
- C08G2150/00—Compositions for coatings
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Abstract
The invention relates to an environment-friendly hard polyurethane spraying material for polyethylene winding prefabricated direct-buried heat-insulation pipes, which comprises a component A and a component B, wherein the component A comprises the following components: polyether polyol, foam stabilizer, water, catalyst and additive; the component B is polymethylene polyphenyl polyisocyanate; the polyether polyol comprises polyether polyol I, polyether polyol II, polyether polyol III and polyether polyol IV; the polyether polyol IV is prepared by using a sucrose initiator, extending a chain by propylene oxide and blocking an end by ethylene oxide, wherein the viscosity is 1000-2000 MPa.s/25 ℃, and the hydroxyl value is 300-500 mgKOH/g. The invention adopts full water foaming, is environment-friendly and meets the future development requirement; through the effective collocation of the polyether glycol and the catalyst, the problems of poor curing performance and brittleness of the all-water rigid polyurethane foaming product are solved; and the problem of poor adhesion between the all-water rigid polyurethane foaming product and the steel pipe is solved by effectively matching the polyether polyol II, the polyether polyol IV and the additive, and the effective contact and heat insulation effects of the heat insulation material and the base material are ensured.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to an environment-friendly rigid polyurethane spraying material for polyethylene-wound prefabricated direct-buried thermal insulation pipes and a preparation method thereof.
Background
With the increasing maturity of the urban central heating and cooling markets, the requirements on the technology, quality, cost and the like of the heat-insulating pipe are also updated and higher. The most important advantages of the polyurethane spraying and winding technology are low cost and better comprehensive performance, and the related standard GB/T34611-2017 is published. With the vigorous promotion of the national policy of environmental protection and energy conservation, the advantages of polyurethane spraying and winding prefabricated direct-buried insulating pipe products are certainly highlighted, and the method has higher popularization value.
The prior patent CN 103159908B 'polyurethane for spraying and winding prefabricated direct-buried insulating pipes' discloses a polyurethane raw material for spraying pipelines, and uses HCFC-141B foaming agent. HCFC-141B has entered the phase of phase-out because of its non-environmental protection, the phase-out time of HCFC-141B in the pipeline industry is 2020.
Water is the cleanest foaming agent, and some manufacturers on the market are developing related products, but the developed products mainly have 2 defects: (1) the sprayed polyurethane is very crisp, and cracks appear through the subsequent process, so that the heat-insulating property is greatly reduced; (2) the adhesion is not good, mainly the adhesion between the steel pipe and the polyurethane and between the polyurethane and the polyurethane is not good, and the phenomena of bag-up and cavities occur; these two points are also the main difficulties and pain points of the industry of all-water rigid polyurethane spraying products.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an environment-friendly rigid polyurethane spraying material for winding polyethylene on a prefabricated direct-buried heat-insulation pipe.
The first purpose of the invention is to provide an environment-friendly rigid polyurethane spraying material for polyethylene winding prefabricated direct-buried heat-insulation pipes, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1: 1-2; the component A comprises the following components in parts by weight: 100 parts of polyether polyol composition, 0.5-2 parts of foam stabilizer, 1.5-3.5 parts of water, 3-7 parts of catalyst and 5-10 parts of additive; the component B is 110-245 parts of polymethylene polyphenyl polyisocyanate;
the polyether polyol composition comprises the following components, by weight, 55-70 parts of polyether polyol I, 10-20 parts of polyether polyol II, 5-10 parts of polyether polyol III and 5-15 parts of polyether polyol IV, wherein the polyether polyol IV is prepared by a sucrose initiator, a propylene oxide chain extender and an ethylene oxide end cap, the viscosity is 1000-2000 MPa-s/25 ℃, and the hydroxyl value is 300-500 mgKOH/g. Specifically, the polyether polyol I is prepared by extending a sucrose initiator and propylene oxide with the viscosity of 2000-4000 MPa.s/25 ℃ and the hydroxyl value of 300-500 mgKOH/g; the polyether polyol II is prepared by extending propylene glycol initiator and propylene oxide with the viscosity of 100-400 MPa.s/25 ℃ and the hydroxyl value of 50-120 mgKOH/g; the polyether polyol III is prepared by extending ethylene diamine initiator and propylene oxide with the viscosity of 1500-2000 MPa.s/50 ℃ and the hydroxyl value of 700-850 mgKOH/g. In the invention, the polyether polyol II is polyether polyol with high molecular weight and low functionality, and the polyether polyol I, the polyether polyol III and the polyether polyol IV are polyether polyol with low molecular weight and high functionality, so that the curing speed of the foam of the polyether polyol composition of the polyurethane spraying material is accelerated and the adhesive property is improved by the synergistic combination of the four polyether polyols.
Specifically, the foam stabilizer is one or more selected from LK665 of air chemical industry, M8805 of Maisted and Ma L6900.
Specifically, the catalyst is a mixture of four catalysts, namely pentamethyldiethylenetriamine, a solution A33 of 33% triethylene diamine diethylene glycol, N-dimethylcyclohexylamine PC8 and a trimerization catalyst K15; thus, the four catalysts are compounded in proportion, and the following synergistic effects can be generated: the catalysis of the foaming, the gel reaction and the black material trimerization reaction can be simultaneously carried out, thereby increasing the strength and the dimensional stability of the foam.
Specifically, the weight parts of the pentamethyldiethylenetriamine, the 33% triethylene diamine diethylene glycol solution A33, the N, N-dimethylcyclohexylamine PC8 and the trimerization catalyst K15 are 0.5-2:1-2.5:0.5-1.5: 1.
Specifically, the additive is AP-01 in the Mylar chart, and is matched with polyether polyol II and polyether polyol IV to help improve the bonding force between the foam and a substrate at low temperature.
The second purpose of the invention is to provide a preparation method of the environment-friendly rigid polyurethane spraying material, which comprises the following steps:
(1) weighing polyether polyol I, polyether polyol II, polyether polyol III, polyether polyol IV, a foam stabilizer, water, a catalyst and an additive according to a mass ratio, and mixing to form a component A; weighing polymethylene polyphenyl polyisocyanate as a component B;
(2) and mixing the component A and the component B, mixing and spraying the mixture on the surface of a steel pipe by a high-pressure spraying machine for foaming and molding, advancing by rotating the steel pipe, and performing layer-by-layer spraying construction to prepare the environment-friendly hard polyurethane spraying material.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention adopts full water foaming, does not contain HCFC-141b foaming agent damaging the ozone layer, does not contain foaming agent such as HFC-245fa and the like which can bring serious greenhouse effect, and is a product which is environment-friendly and meets the future development requirement of the product;
2. through the effective collocation of the polyether glycol I, the polyether glycol II, the polyether glycol III and the polyether glycol IV with the catalyst, the problems of poor curing performance, crisp property and the like of the all-water rigid polyurethane foaming product are solved;
3. and the problem of poor adhesion between the all-water rigid polyurethane foaming product and the steel pipe is solved by effectively matching the polyether polyol II, the polyether polyol IV and the additive, and the effective contact between the heat-insulating material and the base material and the heat-insulating effect are ensured.
Detailed Description
The invention relates to an environment-friendly hard polyurethane spraying material for polyethylene winding prefabricated direct-buried heat-insulation pipes, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1: 1-2; the component A comprises the following components in parts by weight: 100 parts of polyether polyol composition (55-70 parts of polyether polyol I, 10-20 parts of polyether polyol II, 5-10 parts of polyether polyol III and 5-15 parts of polyether polyol IV), 0.5-2 parts of foam stabilizer, 1.5-3.5 parts of water, 3-7 parts of catalyst and 5-10 parts of additive; the component B is 110-245 parts of polymethylene polyphenyl polyisocyanate;
the polyether polyol composition comprises, by weight, 55-70 parts of polyether polyol I, 10-20 parts of polyether polyol II, 5-10 parts of polyether polyol III and 5-15 parts of polyether polyol IV. The foaming agent adopts full water for foaming, does not contain HCFC-141b foaming agent damaging the ozone layer, does not contain foaming agent such as HFC-245fa and the like which can bring serious greenhouse effect, and is a product which is environment-friendly and meets the future development requirement of the product.
The polyether polyol I is prepared by extending a sucrose initiator and propylene oxide with the viscosity of 2000-; the polyether polyol II is prepared by extending propylene glycol initiator and propylene oxide, has the viscosity of 100-400 MPa.s/25 ℃, has the hydroxyl value of 50-120mgKOH/g, and can be one or more of CHE-210 purchased from Changhua chemistry, JH-210 purchased from optimization chemistry and NJ-210 purchased from sentencing Ningwu (in the invention, any one or any combination of the three polyether polyols II is selected, and has no influence on the performance of the polyurethane spraying material); the polyether polyol III is prepared by extending ethylene diamine initiator and propylene oxide with the viscosity of 1500-2000MPa s/50 ℃ and the hydroxyl value of 700-850mgKOH/g, and can be SD403 of cis-Da polyurethane Co., Ltd, cigarette Tai; the polyether polyol IV is prepared from a sucrose initiator, propylene oxide for chain extension and ethylene oxide for end capping, has the viscosity of 1000-2000 MPa.s/25 ℃, the hydroxyl value of 300-500mgKOH/g, and can be SD1033 of cis-polyurethane Co. In the invention, the polyether polyol II is polyether polyol with high molecular weight and low functionality, and the polyether polyol I, the polyether polyol III and the polyether polyol IV are polyether polyol with low molecular weight and high functionality, so that the curing speed of the foam of the polyether polyol composition of the polyurethane spraying material is accelerated and the adhesive property is improved by the synergistic combination of the four polyether polyols.
The foam stabilizer is one or more selected from LK665 of air chemical industry, M8805 of Maillard and Ma chart L6900. In the invention, any one or any combination of the above three foam homogenizing agents is selected, so that the performance of the polyurethane spraying material is slightly influenced.
The catalyst is a mixture of pentamethyldiethylenetriamine, a solution A33 of diethylene glycol containing 33% of triethylene diamine, N-dimethylcyclohexylamine PC8 and a trimerization catalyst K15, and the specific ratio is 0.5-2:1-2.5:0.5-1.5: 1; thus, the four catalysts are compounded in proportion, and the following synergistic effects can be generated: the catalysis of the foaming, the gel reaction and the black material trimerization reaction can be simultaneously carried out, thereby increasing the strength and the dimensional stability of the foam.
The additive is AP-01, purchased from Mayer company; the combination of the polyether polyol and the polyether polyol is beneficial to improving the bonding force between the foam and the base material at low temperature.
The second purpose of the invention is to provide a preparation method of the environment-friendly rigid polyurethane spraying material, which comprises the following steps:
(1) weighing polyether polyol I, polyether polyol II, polyether polyol III, polyether polyol IV, a foam stabilizer, water, a catalyst and an additive according to a mass ratio, and mixing to form a component A; weighing polymethylene polyphenyl polyisocyanate as a component B;
(2) uniformly mixing the component A and the component B, mixing and spraying the mixture on the surface of a steel pipe by a high-pressure spraying machine for foaming and molding, advancing by rotating the steel pipe, and performing layer-by-layer spraying construction to prepare the environment-friendly hard polyurethane spraying material.
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry.
Embodiment 1 this example provides an environment-friendly rigid polyurethane spray coating material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe, wherein the mass ratio of the component A to the component B is 1: 1.5;
wherein, the component A comprises: 100 parts of polyether polyol composition (comprising 60 parts of SD6152, 15 parts of JH210, 10 parts of SD403 and 15 parts of SD1033), 1 part of foam stabilizer M8805, 3.0 parts of blowing agent water, 4 parts of catalyst (1 part of PC5, 1 part of A33, 1 part of PC8 and 1 part of K15), 6 parts of additive AP-01;
component B was 171 parts PM200 (ex Tantawa).
The preparation method of the environment-friendly rigid polyurethane spraying material for winding the polyethylene on the prefabricated direct-buried heat-insulation pipe comprises the following steps:
(1) weighing polyether polyol I, polyether polyol II, polyether polyol III, polyether polyol IV, a foam stabilizer, water, a catalyst and an additive according to a mass ratio, and mixing to form a component A; weighing polymethylene polyphenyl polyisocyanate as a component B;
(2) uniformly mixing the component A and the component B, mixing and spraying the mixture on the surface of a steel pipe by a high-pressure spraying machine for foaming and molding, advancing by rotating the steel pipe, and performing layer-by-layer spraying construction to prepare the environment-friendly hard polyurethane spraying material.
Example 2 this example provides an environmentally friendly rigid polyurethane spray coating material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as that in example 1 except that: the mass ratio of the component A to the component B is 1:1, wherein the component A is not changed, and the added part of the component B is 114 parts.
Example 3 this example provides an environmentally friendly rigid polyurethane spray coating material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as that in example 1 except that: the mass ratio of the component A to the component B is 1:2, wherein the component A is not changed, and the added part of the component B is 228 parts.
Example 4 this example provides an environmentally friendly rigid polyurethane spray coating material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as that in example 1 except that: 100 parts of polyether polyol composition, which comprises 55 parts of SD6152, 20 parts of JH210, 10 parts of SD403 and 15 parts of SD 1033.
Example 5 this example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as that in example 1 except that: 100 parts of polyether polyol composition, which comprises 70 parts of SD6152, 10 parts of JH210, 10 parts of SD403 and 10 parts of SD 1033.
Example 6 this example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as that in example 1 except that: 100 parts of polyether polyol composition, 70 parts of SD6152, 20 parts of JH210, 5 parts of SD403 and 5 parts of SD 1033.
Example 7 this example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as that of example 1 except that: polyether polyol composition 100 parts (70 parts SD6152, 15 parts JH210, 10 parts SD403, 5 parts SD 1033).
Example 8 this example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as that in example 1 except that: polyether polyol composition 100 parts (65 parts SD6152, 14 parts NJ210, 8 parts SD403, 13 parts SD 1033).
Example 9 this example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as that in example 1 except that: the 4 parts of catalyst were added in different proportions (containing 1.5 parts of PC5, 1 part of A33, 1.5 parts of PC8 and 1 part of K15).
Example 10 this example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as that in example 1 except that: the addition ratio of 4 parts of catalyst was varied (containing 1 part of PC5, 2.5 parts of A33, 1 part of PC8 and 1 part of K15).
Example 11 this example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as that of example 1 except that: the addition ratio of 4 parts of catalyst was varied (containing 2 parts of PC5, 2.5 parts of A33, 0.5 parts of PC8 and 1 part of K15).
Example 12 this example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-burried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: the addition part of the additive is 10 parts.
Comparative example 1 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: the mass ratio of the component A to the component B is 1:3, the adding part of the component A is unchanged, and the adding part of the component B is 342 parts.
Comparative example 2 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: the mass ratio of the component A to the component B is 2:1, the adding parts of the component B are unchanged, and the adding parts of the component A are doubled correspondingly.
Comparative example 3 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: polyether polyol composition 100 parts (75 parts SD6152, 5 parts JH210, 3 parts SD403, 17 parts SD 1033).
Comparative example 4 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: polyether polyol composition 100 parts (40 parts SD6152, 20 parts JH210, 20 parts SD403, 20 parts SD 1033).
Comparative example 5 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: 100 parts of polyether polyol composition (containing 50 parts of JH210, 30 parts of SD403 and 20 parts of SD1033)) without adding polyether polyol I.
Comparative example 6 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: 100 parts of polyether polyol composition (comprising 75 parts of SD6152, 10 parts of SD403 and 15 parts of SD1033) are not added with polyether polyol II.
Comparative example 7 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: polyether polyol iii was not added, 100 parts of polyether polyol composition (comprising 75 parts SD6152, 20 parts JH210, 5 parts SD 1033).
Comparative example 8 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: 100 parts of polyether polyol composition (comprising 75 parts of SD6152, 20 parts of JH210 and 5 parts of SD403) are not added with polyether polyol IV.
Comparative example 9 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: no catalyst PC5 was added, and 3 parts of catalyst (comprising 2 parts of A33, 1 part of PC8 and 1 part of K15) were selected.
Comparative example 10 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: catalyst A33 was not added and 3 parts of catalyst (comprising 2 parts of PC5, 1 part of PC8 and 1 part of K15) were selected.
Comparative example 11 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: no catalyst PC8 was added, and 3 parts of catalyst (comprising 2 parts of PC5, 1 part of A33 and 1 part of K15) were selected.
Comparative example 12 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: no catalyst K15 was added, 3 parts of catalyst (comprising 2 parts of PC5, 1 part of A33 and 1 part of PC8) were selected.
Comparative example 13 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-burried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1, using 4 parts of the same catalyst as in example 1 except that: the addition ratio of 4 parts of catalyst was varied (containing 3 parts of PC5, 2 parts of A33, 1 part of PC8 and 2 parts of K15).
Comparative example 14 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-burried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1, using 4 parts of the same catalyst as in example 1 except that: the addition ratio of 4 parts of catalyst was varied (containing 2 parts of PC5, 3 parts of A33, 2 parts of PC8 and 2 parts of K15).
Comparative example 15 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: does not contain any catalyst.
Comparative example 16 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: does not contain the additive AP-01.
Comparative example 17 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-burried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: the additive is not AP-01, and is originated PM300 additive.
Comparative example 18 this comparative example provides an environmentally friendly rigid polyurethane spray material for polyethylene-wrapped prefabricated direct-buried thermal insulation pipe and a method for preparing the same, which is substantially the same as in example 1 except that: the additive is not AP-01, and is originated PM301 additive.
Table 1 application performance data for environmentally friendly rigid polyurethane spray foam insulation in examples 1-12 and comparative examples 1-18:
the test criteria are as follows: density GB/T6343-.
As can be seen from the data of examples 1-3, comparative examples 1-2 and Table 1, each performance parameter satisfies the application requirement when the mass ratio of the component A to the component B is 1: 1-2. In comparative example 1, when the mass ratio of the component A to the component B is 1:3, the black material is excessive, so that the foam is crisp and the adhesion of the base material is very poor, a large amount of cracking occurs in the production process, and the foam and the base material fall off after the subsequent PE winding and extruding process. In comparative example 2, when the mass ratio of the A component to the B component was 1:0.5, the foam was shrunk and the foam could not be tested for physical properties.
As can be seen from the data of examples 1, 4-8 and comparative examples 3-4 and Table 1, the polyether polyol compositions have a ratio of polyether polyol I, polyether polyol II, polyether polyol III and polyether polyol IV of (55-70) to (10-20): (5-10): and (5-15), all performance parameters meet the application requirements. In comparative example 3, when the amount of polyether polyol II was reduced, the foam became brittle and the adhesion to the substrate was very poor, and a large amount of cracking occurred during the production. In comparative example 4, a large amount of cracking occurred during the production, the insulation after application was poor, possibly an excessive amount of polyether polyol III, too many crosslinking points, and poor toughness.
As can be seen from the data of examples 1-12, comparative examples 5-8 and Table 1, the polyether polyol composition must be a blend of four, but none. Comparative example 5 lacks polyether polyol I, the overall strength is low and foam shrinkage occurs. Comparative example 6, without polyether polyol II, the foam became brittle and the adhesion to the substrate was very poor, a large amount of cracking occurred during the production process, and the heat retention after application was poor. Comparative example 7 lacks polyether polyol III, the foam is softer and shrinkage occurs. In comparative example 8, polyether polyol IV was absent, the curing properties of the foam were inferior, the adhesion was not as good as in examples 1 to 12, and the foam showed shrinkage.
As can be seen from the data of example 1, comparative examples 9-12 and Table 1, the balance of the whole foaming system is destroyed and the foam shrinks after the four catalysts are compounded but lack of any catalyst.
The ratios of the four catalysts are particularly important as can be seen from the data of examples 1, 9-11, comparative examples 13-14 and table 1. When the amount of the catalyst is too large, the phenomenon of gun blockage occurs in the spraying process, so that the production efficiency is reduced, and the flatness of the foam is poor. As can be seen from comparative example 15, the foaming rate was very slow without adding a catalyst, and the sprayed material was liquid and drooling, and no more foam could be formed on the surface of the steel pipe.
As can be seen from example 1 and comparative example 16, the importance and specificity of the additive, the additive AP-01 of the present invention was selected, and when no additive was added, the adhesion was slightly poor, the foam at the contact with the substrate was brittle, and the pipe end was debonded. The AP-01 additive improves the foam brittleness of the contact part of polyurethane and a base material, and is possibly helpful to change or reduce the structure of a large amount of urea bonds generated by foaming of an all-water system, so that the polyurethane foam has better bonding strength with the base material. The additives of comparative examples 17-18 are selected, the foam has high brittleness and debonding phenomenon, and the foam has a plurality of cracks through the subsequent production process.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (4)
1. The environment-friendly rigid polyurethane spraying material for winding the polyethylene on the prefabricated direct-buried heat-insulation pipe is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 1: 1-2; the component A comprises the following components in parts by weight: 100 parts of polyether polyol composition, 0.5-2 parts of foam stabilizer, 1.5-3.5 parts of water, 3-7 parts of catalyst and 5-10 parts of additive; the component B is 110-245 parts of polymethylene polyphenyl polyisocyanate;
the polyether polyol composition comprises the following components, by weight, 55-70 parts of polyether polyol I, 10-20 parts of polyether polyol II, 5-10 parts of polyether polyol III and 5-15 parts of polyether polyol IV; the polyether polyol IV is prepared by a sucrose initiator, a propylene oxide chain extender and an ethylene oxide end capping, the viscosity is 1000-2000 MPa-s/25 ℃, and the hydroxyl value is 300-500 mgKOH/g;
the polyether polyol I is prepared by extending a sucrose initiator and propylene oxide with the viscosity of 2000-4000 MPa-s/25 ℃ and the hydroxyl value of 300-500 mgKOH/g;
the polyether polyol II is prepared by extending propylene glycol initiator and propylene oxide with the viscosity of 100-400 MPa.s/25 ℃ and the hydroxyl value of 50-120 mgKOH/g;
the polyether polyol III is prepared by extending ethylene diamine initiator and propylene oxide with the viscosity of 1500-2000 MPa.s/50 ℃ and the hydroxyl value of 700-850 mgKOH/g;
the catalyst is a mixture of four catalysts, namely pentamethyldiethylenetriamine, a solution A33 of 33 percent triethylene diamine diethylene glycol, N-dimethylcyclohexylamine PC8 and a trimerization catalyst K15; the additive is a Michael chart AP-01, and the viscosity of the additive is 50-200 MPa.s/25 ℃.
2. The environmentally friendly rigid polyurethane spray material according to claim 1, wherein: the foam stabilizer is one or more selected from LK665 of air chemical industry, M8805 of Maillard and Ma chart L6900.
3. The environmentally friendly rigid polyurethane spray material according to claim 1, wherein: the weight portion ratio of the pentamethyl diethylene triamine, a diethylene glycol solution A33 of 33 percent triethylene diamine, N-dimethyl cyclohexylamine PC8 and a trimerization catalyst K15 is 0.5-2:1-2.5:0.5-1.5: 1.
4. A process for the preparation of an environmentally friendly rigid polyurethane spray material as claimed in any one of claims 1 to 3, comprising the steps of:
(1) weighing polyether polyol I, polyether polyol II, polyether polyol III, polyether polyol IV, a foam stabilizer, water, a catalyst and an additive according to a mass ratio, and mixing to form a component A; weighing polymethylene polyphenyl polyisocyanate as a component B;
(2) and mixing the component A and the component B, mixing and spraying the mixture on the surface of a steel pipe by a high-pressure spraying machine for foaming and molding, advancing by rotating the steel pipe, and performing layer-by-layer spraying construction to prepare the environment-friendly hard polyurethane spraying material.
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| WO2017085283A1 (en) * | 2015-11-19 | 2017-05-26 | Covestro Deutschland Ag | Method for producing a rigid polyurethane foam |
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| JP2009215386A (en) * | 2008-03-10 | 2009-09-24 | Kao Corp | Method for producing rigid polyurethane foam |
| WO2017085283A1 (en) * | 2015-11-19 | 2017-05-26 | Covestro Deutschland Ag | Method for producing a rigid polyurethane foam |
| CN107915821A (en) * | 2016-10-10 | 2018-04-17 | 万华化学（北京）有限公司 | A kind of polyurethane foam and its preparation method and application |
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