CN103709356B - Polyurethane rigid foam composition, thermal insulation layer and utilidor - Google Patents

Polyurethane rigid foam composition, thermal insulation layer and utilidor Download PDF

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Publication number
CN103709356B
CN103709356B CN201310741891.1A CN201310741891A CN103709356B CN 103709356 B CN103709356 B CN 103709356B CN 201310741891 A CN201310741891 A CN 201310741891A CN 103709356 B CN103709356 B CN 103709356B
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polyether glycol
composition
rigid foam
polyurethane rigid
thermal insulation
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CN103709356A (en
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任建鹏
邸建军
刘小平
李依璇
赖广森
张凯昌
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Beijing Bihai Yunzhi New Material Technology Co., Ltd
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LANGFANG BIHAIZHOU PAINT CO Ltd
BEIJING BSS CORROSION PROTECTION INDUSTRY 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
    • C08G18/08—Processes
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate 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
    • C08G18/4804—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
    • C08G18/28—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
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • 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
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • 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
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon

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  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a kind of polyurethane rigid foam composition, thermal insulation layer and utilidor.This polyurethane rigid foam composition comprises by weight: the polyisocyanates of 95 ~ 230 parts, the polyether glycol of 45 ~ 95 parts, the polyester polyol of 5 ~ 55 parts, appropriate catalyzer and whipping agent; Wherein, polyether glycol comprises the different polyether glycol of at least two kinds of hydroxyl values.This polyurethane rigid foam composition, by polyisocyanates, at least two kinds of polyether glycols and polyester polyol being added by proportioning simultaneously, can adjust the mobility of composition; Form differential responses system by least two kinds of polyvalent alcohols and polyisocyanates, the solidification rate of composition can be adjusted; By the common adjustment of different polyvalent alcohol and isocyanic ester, the levelling of composition and the time of solidification can be mated.And then improve polyurethane rigid foam composition and got rid of de-phenomenon when pipeline sprays by rotary centrifugal force, and the rough phenomenon of pipe insulating layer.

Description

Polyurethane rigid foam composition, thermal insulation layer and utilidor
Technical field
The present invention relates to insulating pipe and manufacture field, in particular to a kind of polyurethane rigid foam composition, thermal insulation layer and utilidor.
Background technology
The structure of hard polyurethane foam insulating pipe mainly comprises working steel tube, hard polyurethane foam thermal insulation layer and polyethylene outer protective pipe from the inside to the outside.Wherein, hard polyurethane foam has the advantages such as density is little, specific tenacity is high, good heat-insulation effect, moulding process are simple.By the feature that the thermal insulation layer that it makes also has erosion resistant, do not absorb water.These advantages make hard polyurethane foam in heat insulating work, particularly receive in prepressing reserving works and favor widely.At present, hard polyurethane foam insulating pipe is widely applied in fields such as district heating, district cooling, oil and gas, industrial liquid transmission and boats and ships fluid transports.
In existing polyurethane heat-preserving pipeline, the production technique of thermal insulation layer mainly contains " two-step approach ", " single stage method " and " spraying method ".Wherein, the concrete operation step of " spraying method " is as follows: rotated with certain rotating speed by pipeline to be painted, make the shower nozzle of polyurethane composition carry out unidirectional relative movement with certain speed along the axis of pipeline to be painted, carry out pipeline spraying with this.Owing to adopting " spraying method " to have the advantage such as uniform in foaming, production efficiency height, it is made to get the attention in the preparation of polyurethane heat-preserving pipeline.But the polyurethane rigid foam composition being applicable to pipeline spraying is little, and this is mainly caused by following reason:
When the flow time of polyurethane rigid foam composition is too short, set time is time long, makes the reactive force of composition inside lower after the rapid levelling of composition because having little time solidification.Lower inertial forces make composition very easily get rid of by the centrifugal force that produces because pipeline rotates de-.When the flow time of polyurethane rigid foam composition is long, set time, time too short, composition had little time levelling with regard to rapid solidification, make composition very easily occur caking, and then cause thermal insulation layer to occur rough phenomenon.On this basis, how mating flow time and the set time of polyurethane rigid foam composition, is the key ensureing pipe insulating layer spraying effect.
Summary of the invention
The present invention aims to provide a kind of polyurethane rigid foam composition, thermal insulation layer and utilidor, to provide a kind of polyurethane rigid foam composition being applicable to pipeline spraying method.
To achieve these goals, according to an aspect of the present invention, provide a kind of polyurethane rigid foam composition, it comprises by weight: the polyisocyanates of 95 ~ 230 parts, the polyether glycol of 45 ~ 95 parts, the polyester polyol of 5 ~ 55 parts, appropriate catalyzer and whipping agent; Wherein, polyether glycol comprises the different polyether glycol of at least two kinds of hydroxyl values.
Further, the polyether glycol II of above-mentioned polyether glycol comprises 35 ~ 60 parts of hydroxyl values to be polyether glycol I, 10 ~ 20 parts of hydroxyl values of 400 ~ 470mgKOH/g be 360 ~ 500mgKOH/g and 0 ~ 30 part of hydroxyl value are the polyether glycol III of 720 ~ 810mgKOH/g.
Further, its by weight, the consumption of catalyzer is 1.6 ~ 12.5 parts, and the consumption of whipping agent is 5 ~ 37 parts.
Further, it comprises by weight: the described polyester polyol of the described polyether glycol III, 5 ~ 35 parts of the described polyether glycol II, 5 ~ 20 parts of the described polyisocyanates of 100 ~ 180 parts, the described polyether glycol of 45 ~ 55 parts I, 15 ~ 20 parts, the described catalyzer of 1.6 ~ 12.5 parts and the described whipping agent of 10 ~ 30.1.
Further, above-mentioned polyether glycol I is Sucrose polyethers polyvalent alcohol with polyether glycol II; Polyether glycol III is diamines polyether glycol; Polyester polyol is aromatic polyester polyol and/or rosin polyester polyhydric-alcohol.
Further, the functionality of above-mentioned polyisocyanates is 2.6 ~ 2.7, and preferred isocyanate is the many phenyl isocyanate of polymethine.
Further, above-mentioned catalyzer comprise 0.5 ~ 4.2 part work the dibutyl tin laurate sending out a catalyzer, the gel catalyst of 0.5 ~ 4 part, the catalyst for trimerization of 0.5 ~ 4 part and 0.1 ~ 0.3 part; Preferably, work the mixing solutions sending out catalyzer to be pentamethyl-diethylenetriamine and carbon content be the alcohol of C2 ~ C5, or the mixture of pentamethyl-diethylenetriamine and dimethylcyclohexylamine; The mixing solutions of gel catalyst to be triethylene diamine and carbon content the be alcohol of C2 ~ C5, or the mixture of triethylene diamine and N, N-dimethylethanolamine; Catalyst for trimerization is Potassium ethanoate and/or 1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine.
Further, above-mentioned whipping agent is a fluorine ethylene dichloride, or the mixture of a fluorine ethylene dichloride and water.
Further, above-mentioned composition also comprises by weight: the equal infusion of 1 ~ 3 part, and described equal infusion is siloxane type surfactants, is preferably one or more in LK665, AK8801, AK8805, AK8803 and AK8812.
According to a further aspect in the invention, provide a kind of thermal insulation layer, it is formed through spraying, solidification by above-mentioned polyurethane rigid foam composition.
According to a further aspect in the invention, additionally provide a kind of utilidor, comprise thermal insulation layer, this thermal insulation layer is above-mentioned thermal insulation layer.
Apply polyurethane rigid foam composition of the present invention, pipe insulating layer and utilidor.By polyisocyanates, the polyether glycol with different hydroxyl value content and polyester polyol being added by proportioning simultaneously, the mobility of polyurethane rigid foam composition can be adjusted; Meanwhile, form differential responses system by the polyvalent alcohol and polyisocyanates adopting different hydroxyl value, the solidification rate of polyurethane rigid foam composition can be adjusted; Further, by the common adjustment of different polyvalent alcohol and isocyanic ester, flow time and the set time of composition can be mated.The coupling of this set time and flow time, effectively can avoid polyurethane rigid foam composition when pipeline sprays, cause composition inertial forces too low, and then got rid of de-phenomenon by the rotary centrifugal force of pipeline because levelling is too fast or set time is oversize.Meanwhile, avoid the composition rapid solidification having little time levelling and to lump the rough phenomenon of pipe insulating layer caused, further improve the pipeline spraying effect of composition.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
In polyurethane rigid foam composition, the curing reaction time of polyvalent alcohol and polyisocyanates receives the impact of reactive functionality ratio and catalyst content in system.Meanwhile, the flow time of composition in pipeline spraying process receives the impact of the content of each component in composition.Above-mentioned set time and flow time directly can affect the pipeline spraying effect of composition.When the flow time of composition is too short, set time is time long, because the rotation of pipeline can produce certain centrifugal force, makes composition be got rid of de-because having little time solidification by this centrifugal force; When the flow time of composition is long, time too short, composition had little time levelling and just there occurs solidification set time, made composition easily lump, and then thermal insulation layer can be caused to occur rough phenomenon.
In order to the problem that the flow time and being difficult to set time solving composition when the employing spraying method proposed in background technology prepares pipe insulating layer mates, inventor provides a kind of polyurethane rigid foam composition, and it comprises the polyisocyanates of 95 ~ 230 parts, the polyether glycol of 45 ~ 95 parts, the polyester polyol of 5 ~ 55 parts, appropriate catalyzer and whipping agent by weight; Polyether glycol comprises the different polyether glycol of at least two kinds of hydroxyl values.
In this polyurethane rigid foam composition provided by the present invention, based on different material mobility between difference, proportionally with the addition of polyisocyanates simultaneously, there is polyether glycol and the polyester polyol of different hydroxyl value content, to adjust the flow time of polyurethane rigid foam composition.And by being added from the polyether glycol and polyester polyol with different hydroxyl value content are collaborative by polyisocyanates, form different curing reaction systems to regulate the set time of polyurethane rigid foam composition.Further, by the common adjustment of different polyvalent alcohol and isocyanic ester, to mate flow time and the set time of composition.This polyurethane rigid foam composition provided by the present invention is by mating flow time and the set time of composition, can can reduce when pipeline sprays and be got rid of de-incidence because of the rotation of pipeline, in time complete curing reaction after can making composition levelling simultaneously, and then avoid pipe insulating layer to occur rough problem.
One of the present invention preferred embodiment in, polyether glycol II, 0 ~ 30 part of hydroxyl value of polyether glycol comprises 35 ~ 60 parts of hydroxyl values to be polyether glycol I, 10 ~ 20 parts of hydroxyl values of 400 ~ 470mgKOH/g be 360 ~ 500mgKOH/g is the polyether glycol III of 720 ~ 810mgKOH/g.In above-mentioned composition, add by scope is collaborative in specific proportions by the polyether glycol of different hydroxyl value, can make more mate with flow time set time.And then make the spraying effect of composition more excellent.
In the preferred embodiment of one of the present invention, by weight, the consumption of catalyzer is 1.6 ~ 12.5 parts to above-mentioned composition, and the consumption of whipping agent is 5 ~ 37 parts.In above-mentioned composition, by adding appropriate catalyzer and whipping agent further, be conducive to the set time and the flow time that adjust composition further, make both more mate, and then meet employing spraying method formation polyurethane rigid foam composition to flow time and the requirement of set time.
In a kind of further preferred embodiment of the present invention, above-mentioned composition comprises the polyisocyanates of 100 ~ 180 parts, the polyether glycol III of polyether glycol II, 5 ~ 20 parts of the polyether glycol I, 15 ~ 20 parts of 45 ~ 55 parts and the polyester polyol of 5 ~ 35 parts, the catalyzer of 1.6 ~ 12.5 parts and the whipping agent of 10.1 ~ 30.1 by weight.The component of above-mentioned weight part scope is conducive to the polyurethane rigid foam composition forming flow time and more mate set time, and then can make prepared pipe insulating layer surface smooth even more.
In above-mentioned polyurethane rigid foam composition provided by the present invention, the various polyether glycols used select suitable raw material according to hydroxyl quantity.More preferably, optional polyether glycol I is Sucrose polyethers polyvalent alcohol with polyether glycol II, and wherein polyether glycol I includes but not limited to Sucrose polyethers polyvalent alcohol 4110(hydroxyl value 430-470mgKOH/g) and/or Sucrose polyethers polyvalent alcohol 835(hydroxyl value 420-480mgKOH/g).Polyether glycol II includes but not limited to Sucrose polyethers polyvalent alcohol 380() and/or Sucrose polyethers polyvalent alcohol 680(hydroxyl value 440-480mgKOH/g).Optional polyether glycol III is diamines polyether glycol, and it includes but not limited to diamines polyether glycol 403(hydroxyl value 735-805mgKOH/g).In above-mentioned polyurethane rigid foam composition provided by the present invention, the not specific requirement of optional polyester polyol, it includes but not limited to aromatic polyester polyol and/or rosin polyester polyhydric-alcohol.Wherein aromatic polyester polyol includes but not limited to aromatic polyester polyol 3152.Rosin polyester polyhydric-alcohol includes but not limited to rosin polyester polyhydric-alcohol 800.The above-mentioned raw materials that the present invention is above-mentioned used is commercially available prod, and wherein Sucrose polyethers polyvalent alcohol 680 and rosin polyester polyhydric-alcohol 800 are that Shaoxing Hengfeng urethane company limited produces.
As long as joined by different types of polyol phase lap in the present invention, set time and the flow time of polyurethane rigid foam composition just can be adjusted.In employing above-mentioned a few class polyol phase lap timing, the set time being conducive to making polyurethane rigid foam composition in pipeline spraying process and flow time more mate, and then improve the effect of pipeline spraying.
In above-mentioned polyurethane rigid foam composition provided by the present invention, the polyisocyanates that can adopt not specific requirement, as long as wherein comprise isocyanate group.The functionality of preferred above-mentioned polyisocyanates is 2.6 ~ 2.7.Adopt functionality to be the polyisocyanates of 2.6 ~ 2.7, the over-all propertieies such as the compressive strength of formed polyurethane insulation coating and density can be ensured on the one hand, set time and the flow time of composition can be coordinated on the other hand.More preferably isocyanic ester is the many phenyl isocyanate of polymethine.
In above-mentioned polyurethane rigid foam composition provided by the present invention, operable catalyzer has multiple, as long as can promote each raw material reaction.In the preferred embodiment of the present invention, the catalyzer in composition comprise 0.5 ~ 4.2 part work the dibutyl tin laurate sending out a catalyzer, the gel catalyst of 0.5 ~ 4 part, the catalyst for trimerization of 0.5 ~ 4 part and 0.1 ~ 0.3 part.In this preferred implementation, mutually arranged in pairs or groups by dissimilar catalyzer, effectively can adjust the solidification rate of each curing system in above-mentioned polyurethane rigid foam composition, further the set time of adjustment composition.The polyurethane rigid foam composition adopting above-mentioned catalyzer to be formed, when being carried out pipeline spraying, polyurethane rigid foam composition can be solidified gradually in the process of levelling, and then can improve spray efficiency and the spraying effect of pipe insulating layer.
In above-mentioned polyurethane rigid foam composition provided by the present invention, send out catalyzer for above-mentioned and adopt conventional materials, it preferably includes but is not limited to the mixing solutions that pentamethyl-diethylenetriamine and carbon content are the alcohol of C2 ~ C5, or the mixture of pentamethyl-diethylenetriamine and dimethylcyclohexylamine; Above-mentioned gel catalyst includes but not limited to that triethylene diamine and carbon content are the mixing solutions of the alcohol of C2 ~ C5, or the mixture of triethylene diamine and N, N-dimethylethanolamine; Above-mentioned catalyst for trimerization includes but not limited to Potassium ethanoate and/or 1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine.Adopt the polyurethane rigid foam composition that above-mentioned catalyzer is formed, it is in pipeline spraying process, and flow time can mate more with set time.And then composition can be impelled more stable in pipeline spraying process, and formed pipe insulating layer is impelled to have more excellent over-all properties.
In above-mentioned composition provided by the present invention, its whipping agent can be selected according to the kind of reactant.Preferably, whipping agent is a fluorine ethylene dichloride, or the mixture of a fluorine ethylene dichloride and water.More preferably, whipping agent comprises a fluorine ethylene dichloride of 5 ~ 35 parts and the water of 0.1 ~ 2 part by weight.Adopt this whipping agent, its expansion rate can be utilized to adjust the mobility of composition, and then mate flow time and the set time of composition, ensure the spraying effect of composition.
In the preferred embodiment of the present invention, above-mentioned polyurethane rigid foam composition also comprises the equal infusion of 1 ~ 3 part, more preferably above-mentioned equal infusion is siloxane type surfactants, one or more more preferably in LK665 (AirproductsandchemicalsInc), AK8801 (Jiangsu Maysta Chemical Co., Ltd.), AK8805 (Jiangsu Maysta Chemical Co., Ltd.), AK8803 (Jiangsu Maysta Chemical Co., Ltd.) and AK8812 (Jiangsu Maysta Chemical Co., Ltd.).Above-mentioned equal infusion is added in polyurethane rigid foam composition, distribution of cells in thermal insulation layer can be impelled more even, and then ensure the over-all properties such as compressive strength of thermal insulation layer.
Meanwhile, additionally provide a kind of thermal insulation layer in the present invention, this thermal insulation layer is formed through spraying, solidification by above-mentioned polyurethane rigid foam composition.The smooth surface of this pipe insulating layer, has higher density, compressive strength and rate of closed hole, and has lower thermal conductivity and water-intake rate, and its over-all properties is more excellent.
In addition, additionally provide a kind of utilidor in the present invention, it comprises thermal insulation layer, and this thermal insulation layer is above-mentioned pipe insulating layer.This utilidor has excellent over-all properties, and its heat-insulating property is better, and owing to adopting spraying method directly to prepare, its production efficiency is higher.
Above-mentioned polyurethane rigid foam composition provided by the present invention is by forming spraying slurry by each component mixing, when forming the thermal insulation layer of utilidor, preferably, the linear velocity that in above-mentioned spraying process, pipeline rotates is 94mm ± 18mm/s, the speed of relative movement of spraying material head and pipeline to be painted is 1m ± 0.1m/min, and the pre-heating temperature of each material is 70 ± 2 DEG C.
Be described in further detail the present invention below in conjunction with specific embodiment, these embodiments can not be interpreted as restriction the present invention scope required for protection.
Embodiment 1
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Polyether glycol 4110 60
Sucrose polyethers polyvalent alcohol 380 35
Diamines polyether glycol 403 0
Rosin polyester polyhydric-alcohol 800 5
Water 0
One fluorine ethylene dichloride 37
Concentration is the pentamethyl-diethylenetriamine/ethanolic soln of 33wt% 4.5
Potassium ethanoate 4.1
Weight ratio is triethylene diamine/N, the N-dimethyl ethanol amine mixt of 4:1 4
Dibutyl tin laurate 0.05
Equal infusion LK665 0
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 230
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar is as follows: rotated with the rotating speed of 6r/min on fixed support by pipeline to be painted (DN300).Adopt Graco H-VR spraying machine, composition is heated to 70 DEG C.Then, spraying material head is arranged apart from pipe surface 1m place to be painted, and make spraying material head along the axial direction due of pipeline with the unidirectional relative movement of the speed of 1m ± 0.1m/min, so that above-mentioned composition is sprayed into pipeline external surface.Wherein, steel tube surface temperature is 20 DEG C, defines pipe insulating layer after once shaped at pipe surface.
Embodiment 2
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Sucrose polyethers polyvalent alcohol 835 30
Sucrose polyethers polyvalent alcohol 680 15
Diamines polyether glycol 403 0
Aromatic polyester polyol 3152 55
Water 0
One fluorine ethylene dichloride 37
Weight ratio is the pentamethyl-diethylenetriamine/dimethyleyelohexane amine mixt of 4:1 0.6
1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine 0.4
Concentration is the triethylene diamine/butanol solution of 33wt% 0.3
Dibutyl tin laurate 0.05
Equal infusion LK665 0
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 95
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar as described in Example 1.
Embodiment 3
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Polyether glycol 4110 60
Sucrose polyethers polyvalent alcohol 680 10
Diamines polyether glycol 403 0
Rosin polyester polyhydric-alcohol 800 30
Water 0
One fluorine ethylene dichloride 5
Concentration is the pentamethyl-diethylenetriamine/ethanolic soln of 33wt% 2.5
Potassium ethanoate 0.5
Weight ratio is triethylene diamine/N, the N-dimethyl ethanol amine mixt of 3:1 0.5
Dibutyl tin laurate 0.3
Equal infusion AK8801 0
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 230
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar as described in Example 1.
Embodiment 4
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Polyether glycol 4110 35
Sucrose polyethers polyvalent alcohol 680 20
Diamines polyether glycol 403 30
Aromatic polyester polyol 3152 15
Water 0
One fluorine ethylene dichloride 5
Weight ratio is the pentamethyl-diethylenetriamine/dimethyleyelohexane amine mixt of 4:1 0.5
Weight ratio is Potassium ethanoate/1 of 1:2,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine mixture 0.5
Concentration is the triethylene diamine/butanol solution of 33wt% 0.5
Dibutyl tin laurate 0.1
Equal infusion AK8801 0
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 95
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar as described in Example 1.
Embodiment 5
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Polyether glycol 4110 55
Sucrose polyethers polyvalent alcohol 680 20
Diamines polyether glycol 403 20
Rosin polyester polyhydric-alcohol 800 5
Water 2
One fluorine ethylene dichloride 8
Concentration is the pentamethyl-diethylenetriamine/ethanolic soln of 33wt% 0.8
Potassium ethanoate 0.6
Weight ratio is triethylene diamine/N, the N-dimethyl ethanol amine mixt of 4:1 0.5
Dibutyl tin laurate 0.1
Equal infusion AK8805 3
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 180
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar as described in Example 1.
Embodiment 6
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Polyether glycol 4110 45
Sucrose polyethers polyvalent alcohol 680 15
Diamines polyether glycol 403 5
Rosin polyester polyhydric-alcohol 800 35
Water 1
One fluorine ethylene dichloride 29.1
Concentration is the pentamethyl-diethylenetriamine/isoamyl alcohol of 33wt% 4.2
Potassium ethanoate 4
Weight ratio is triethylene diamine/N, the N-dimethyl ethanol amine mixt of 2:1 4
Dibutyl tin laurate 0.3
Equal infusion AK8803 3
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 100
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar as described in Example 1.
Embodiment 7
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Polyether glycol 4110 40
Sucrose polyethers polyvalent alcohol 680 20
Diamines polyether glycol 403 10
Aromatic polyester polyol 3152 30
Water 0.1
One fluorine ethylene dichloride 15
Weight ratio is the pentamethyl-diethylenetriamine/dimethyleyelohexane amine mixt of 3:2 2.5
Weight ratio is Potassium ethanoate/1 of 2:1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine mixture 1.5
Concentration is the triethylene diamine/propanol solution of 33wt% 1.5
Dibutyl tin laurate 0.1
Equal infusion AK8803 1.0
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 120
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar as described in Example 1.
Embodiment 8
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Polyether glycol 4110 50
Sucrose polyethers polyvalent alcohol 680 15
Diamines polyether glycol 403 15
Aromatic polyester polyol 3152 20
Water 0.1
One fluorine ethylene dichloride 15
Weight ratio is the pentamethyl-diethylenetriamine/dimethyleyelohexane amine mixt of 3:2 3
Weight ratio is Potassium ethanoate/1 of 2:1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine mixture 2
Concentration is the triethylene diamine/methanol solution of 33wt% 2
Dibutyl tin laurate 0.1
Equal infusion AK8812 1.5
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 120
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar as described in Example 1.
Comparative example 1
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Polyether glycol 4110 55
Sucrose polyethers polyvalent alcohol 680 5
Diamines polyether glycol 403 40
Aromatic polyester polyol 3152 0
Water 0
One fluorine ethylene dichloride 10
Weight ratio is the pentamethyl-diethylenetriamine/dimethyleyelohexane amine mixt of 1:2 2
Weight ratio is Potassium ethanoate/1 of 3:2,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine mixture 5
Concentration is the triethylene diamine/butanol solution of 33wt% 5
Dibutyl tin laurate 0
Equal infusion AK8812 4
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 90
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar as described in Example 1.
Comparative example 2
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Polyether glycol 4110 0
Sucrose polyethers polyvalent alcohol 680 85
Diamines polyether glycol 403 0
Aromatic polyester polyol 3152 15
Water 0.1
One fluorine ethylene dichloride 40
Weight ratio is the pentamethyl-diethylenetriamine/dimethyleyelohexane amine mixt of 2:3 0.5
Weight ratio is Potassium ethanoate/1 of 1:3,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine mixture 0.5
Concentration is the triethylene diamine/methanol solution of 70wt% 0.5
Dibutyl tin laurate 3
Equal infusion AK8812 3
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 240
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar as described in Example 1.
Comparative example 3
Configuration polyurethane rigid foam composition, and is placed in material spraying machine stand-by, its component and proportioning as follows:
Component Weight part
Polyether glycol 4110 10
Sucrose polyethers polyvalent alcohol 680 28
Diamines polyether glycol 403 60
Aromatic polyester polyol 3152 2
Water 0.3
One fluorine ethylene dichloride 30
Weight ratio is the pentamethyl-diethylenetriamine/dimethyleyelohexane amine mixt of 1:1 10
Weight ratio is Potassium ethanoate/1 of 1:4,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine mixture 1
Concentration is the triethylene diamine/methanol solution of 33wt% 1
Dibutyl tin laurate 1
Equal infusion 0.2
Functionality is the many phenyl isocyanate of polymethine of 2.6 ~ 2.7 80
Utilize above-mentioned polyurethane rigid foam composition, adopt spraying method to prepare thermal insulation layer at pipe surface, concrete grammar as described in Example 1.
According to the measuring method in " CJ/T114-2000 high-density polyethylene external protective pipe urethane foam prefabricated direct-buried thermal insulation pipe " and requirement, pipe insulating layer performance prepared in above-described embodiment and comparative example is characterized, characterization result as shown in Table 1:
Table one
From the data of above-described embodiment and comparative example, can find out, the above embodiments of the present invention achieve following technique effect: adopt the thermal insulation layer prepared by the method in above-mentioned comparative example, its surface irregularity, its density and compressive strength and unbalanced, fluctuate all in the larger context; And adopting the thermal insulation layer prepared by method of the above embodiment of the present invention, its surfacing, skinning is smooth, can directly at its Surface coating polyethylene outer protective pipe.
Especially, adopt thermal insulation layer prepared by the method for the embodiment of the present invention, it has higher density, compressive strength and rate of closed hole, lower water-intake rate and thermal conductivity.
It can thus be appreciated that, adopt polyurethane rigid foam composition provided by the present invention, spraying method can be utilized to prepare the thermal insulation layer of pipeline.Adopt polyurethane rigid foam composition provided by the present invention through spraying, solidify the pipe insulating layer formed, its over-all properties is more outstanding.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (11)

1. a polyurethane rigid foam composition, it is characterized in that, comprise by weight: the hydroxyl value of the polyisocyanates of 100 ~ 180 parts, the hydroxyl value of 45 ~ 55 parts to be the hydroxyl value of the polyether glycol I, 15 ~ 20 parts of 400 ~ 470mgKOH/g the be polyether glycol II, 5 ~ 20 parts of 360 ~ 500mgKOH/g is the polyester polyol of the polyether glycol III, 5 ~ 35 parts of 720 ~ 810mgKOH/g, the catalyzer of 1.6 ~ 12.5 parts and the whipping agent of 10 ~ 30.1.
2. composition according to claim 1, is characterized in that, described polyether glycol I is Sucrose polyethers polyvalent alcohol with described polyether glycol II; Described polyether glycol III is diamines polyether glycol; Described polyester polyol is aromatic polyester polyol and/or rosin polyester polyhydric-alcohol.
3. composition according to claim 1, is characterized in that, the functionality of described polyisocyanates is 2.6 ~ 2.7.
4. composition according to claim 3, is characterized in that, described isocyanic ester is the many phenyl isocyanate of polymethine.
5. composition according to claim 1, is characterized in that, described catalyzer comprise 0.5 ~ 4.2 part work the dibutyl tin laurate sending out a catalyzer, the gel catalyst of 0.5 ~ 4 part, the catalyst for trimerization of 0.5 ~ 4 part and 0.1 ~ 0.3 part.
6. composition according to claim 5, is characterized in that, described the mixing solutions sending out catalyzer to be pentamethyl-diethylenetriamine and carbon content be the alcohol of C2 ~ C5, or the mixture of pentamethyl-diethylenetriamine and dimethylcyclohexylamine; The mixing solutions of described gel catalyst to be triethylene diamine and carbon content the be alcohol of C2 ~ C5, or the mixture of triethylene diamine and N, N-dimethylethanolamine; Described catalyst for trimerization is Potassium ethanoate and/or 1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine.
7. composition according to claim 1, is characterized in that, described whipping agent is a fluorine ethylene dichloride, or the mixture of a fluorine ethylene dichloride and water.
8. composition according to claim 1, is characterized in that, described composition also comprises by weight: the equal infusion of 1 ~ 3 part, and described equal infusion is siloxane type surfactants.
9. composition according to claim 8, is characterized in that, described equal infusion is one or more in LK665, AK8801, AK8805, AK8803 and AK8812.
10. a thermal insulation layer, is characterized in that, the polyurethane rigid foam composition of described thermal insulation layer according to any one of claim 1 to 9 forms through spraying, solidification.
11. 1 kinds of utilidors, comprise thermal insulation layer, it is characterized in that, described thermal insulation layer is thermal insulation layer according to claim 10.
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CN106632967A (en) * 2015-10-29 2017-05-10 中国石油化工股份有限公司 Polyurethane composition for thermal-insulation pipeline
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