CN106193437A - Cast polyurethane sandwich color steel warming plate and manufacture forming method thereof - Google Patents

Cast polyurethane sandwich color steel warming plate and manufacture forming method thereof Download PDF

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Publication number
CN106193437A
CN106193437A CN201610627253.0A CN201610627253A CN106193437A CN 106193437 A CN106193437 A CN 106193437A CN 201610627253 A CN201610627253 A CN 201610627253A CN 106193437 A CN106193437 A CN 106193437A
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polyurethane
inorganic hybridization
color steel
melamine
warming plate
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CN201610627253.0A
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Chinese (zh)
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CN106193437B (en
Inventor
王洪波
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Chongqing pine Technology Development Co., Ltd.
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Changzhou Poly Energy Saving Technology Co Ltd
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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/26—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups
    • E04C2/284—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating
    • E04C2/292—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating composed of insulating material and sheet metal
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3897—Low-molecular-weight compounds having heteroatoms other than oxygen containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

nullCast polyurethane sandwich color steel warming plate and manufacture forming method thereof，Belong to flame retardant polyurethane energy-saving material to produce and energy-saving building technology field，It is etherified melmac with high temperature resistant inorganic hydridization melmac polyhydric alcohol or polyhydric alcohol、Emulsifying agent、Composite catalyst、Phosphate flame retardant、Foaming agent，If water or waterglass are main raw material(s)，Agitated dispersion，Prepare combined polyether，Then with polymeric isocyanate MDI at panel machine、Flush coater、Foam on casting machine，Obtain environment-friendly type full water foamed B1 level flame retardant inorganic hydridization polyurethane with melamine rigid foam material，Hard polyurethane foam thermal insulation clamp sandwich layer is formed between inorganic hybridization polyurethane with melamine rigid foam material cast inner panel and outside plate，The rigid foam material of patent of the present invention does not contains low boiling hydrocarbon compound fluorochlorohydrocarbon and HCFC compounds，Use Water blown，Do not damage the ozone layer、Do not produce greenhouse effect，Environmental protection，Fire resistance improves at least 20%，Excellent fireproof performance，Its oxygen index (OI) is more than 30%.

Description

Cast polyurethane sandwich color steel warming plate and manufacture forming method thereof
Technical field
The invention belongs to flame retardant polyurethane energy-saving material produce and energy-saving building technology field, particularly to polyurethane sandwich Color steel warming plate and its be manufactured into type method.
Background technology
China is the big country that climate characteristic is complicated, such as the Northeast of severe cold, and the River of summer hot cold, This makes the energy consumption of China's building materials the biggest.The winter warming etc. of northern area, its energy consumption accounts for whole nation total energy consumption 27.3%.But due to the problem of material, technology and technique, China's traditional architecture unit are heating energy consumption is weather in the world 2-3 times of the developed country that condition is close.Country promulgate Medium-and Long-Term Plan for Conserving Energy Resources regulation " 13. five " period newly-built Building wants strict implement energy conservation standard, and existing building progressively to be implemented adiabatic heat-insulation transformation simultaneously.Carry out the joint of 65% comprehensively Energy standard, the energy conservation standard of 75% is carried out in a line city.
The heat insulating energy saving material that China uses at present mainly includes following several: foam type insulation material, composition silicate Insulation material, heat-insulating calcium silicate product insulation material.
The foam type insulation material used at home is mainly EPS insulation material；And polyurethane (PU) insulation material and EPS Insulation material is compared, and heat conductivity is lower, and the heat insulation effect of the PU rigid foam that 50mm is thick is equivalent to 80-100mm thickness EPS.Particularly when north cold area realizes energy-conservation 65%, EPS seam is leaked, and there is serious freeze thawing phenomenon, comes off existing As seriously.
Ordinary rigid polyurethane foam plastics typically uses low boiling hydrocarbon compound fluorochlorohydrocarbon (F11,141B) as sending out Infusion, but this compounds of discovered in recent years is the arch-criminal destroying earth's ozone layer.HCFC (HCFC) class also has one Fixed ozone remove function and generation greenhouse effect, so original polyurethane foam system must be substituted, therefore full water is sent out Bubble technology increasingly receives the favor of people.
And commonly Water-Blown Rigid Polyurethane Foams exists many not enough, as system viscosity is too big, poor fluidity, Foaming is uneven and causes abscess thick, and heat conductivity is bigger than normal, foams embrittlement etc..
Summary of the invention
In order to solve prior art exist the problems referred to above, the invention provides cast polyurethane sandwich color steel warming plate and It manufactures forming method, is etherified tripolycyanamide with high temperature resistant inorganic hydridization melmac polyhydric alcohol or inorganic hybridization polyhydric alcohol Resin, emulsifying agent, composite catalyst, phosphate flame retardant, foaming agent, if water or waterglass are main raw material(s), agitated point Dissipate, prepare full water foamed B1 level flame melamine polyurethane plate respectively, spray, pour into a mould combined polyether, then be polymerized different Cyanate MDI foams on panel machine, flush coater, casting machine, obtains environment-friendly type full water foamed B1 level flame retardant inorganic hydridization trimerization Cyanamide polyurethane rigid foam material, is hard polyurethane foam thermal insulation clamp sandwich layer between inner panel and outside plate, hard polyurethane foam thermal insulation clamp sandwich layer Formed by the cast of inorganic hybridization polyurethane with melamine rigid foam material.
The technical solution adopted in the present invention is as follows:
Cast polyurethane sandwich color steel warming plate, including inner panel and outside plate, is characterized in that: between described inner panel and outside plate be Hard polyurethane foam thermal insulation clamp sandwich layer, described hard polyurethane foam thermal insulation clamp sandwich layer is by inorganic hybridization polyurethane with melamine rigid foam material Cast is formed；
Described inorganic hybridization polyurethane with melamine rigid foam material by inorganic hybridization polyurethane with melamine combined polyether with Polymeric isocyanate foaming is made；
Described inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula is as follows:
Inorganic hybridization melmac polyhydric alcohol
Or
Described inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula is as follows:
Inorganic hybridization melmac polyhydric alcohol
Described inner panel and outside plate are sheet metal, and described sheet metal is color steel.
The thickness of described hard polyurethane foam thermal insulation clamp sandwich layer is 0.5-50cm.
Described hard polyurethane foam thermal insulation clamp sandwich layer and inner panel, the combination of outside plate are and directly solidify bonding, and cohesive force is more than 100Kpa。
Described emulsifying agent is silicone oil, and described silicone oil is the silicone oil that hard bubbles.
Described composite catalyst is potassium acetate, five methyl diethylentriamine, 1,3,5-tri-(dimethylamino-propyl) hexahydro Triazine, trimethyl-N-2 hydroxypropyl caproic acid, triethylenediamine, N, two in accelerine or dibutyl tin laurate Plant or several.
Described fire retardant is phosphate ester, and described phosphate ester is tricresyl phosphate (1-chloro-2-propyl group) ester, tricresyl phosphate (2,3-bis- Chloropropyl) one or both in ester, the viscosity of described phosphate ester is less than 300Pa s.
Described inorganic hybridization melmac polyol molecule structure is as follows:
X in described molecular structure is inorganic hybridization element, including the one in B or Sb；
R in described molecular structure is-(CH2)nOH or-(CH2)mO(CH2)mOH or
-(OCH2CH2CH2CH3)kOH or-O (CH2)pCH(OH)CH2OH wherein 2≤n≤6,2≤m≤6,2≤p≤6,2 ≤k≤41。
Described inorganic hybridization polyhydric alcohol etherificate melmac molecular structure is as follows:
X in described molecular structure is inorganic hybridization element, including the one in B or Sb；
R in described molecular structure is-(CH2)nOH or-(CH2)mO(CH2)mOH or
-(OCH2CH2CH2CH3)kOH or-O (CH2)PCH(OH)CH2OH wherein 2≤n≤6,2≤m≤6,2≤p≤6,2 ≤k≤41。
The manufacture forming method of cast polyurethane sandwich color steel warming plate, it is characterised in that: include step in detail below:
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components being added separately in mixing kettle, room temperature stirs Mix dispersion 2-4 hour, filter out trace mechanical admixture, obtain inorganic hybridization polyurethane with melamine combined polyether；
(2) moulding by casting
By the inorganic hybridization polyurethane with melamine combined polyether that obtains in step (1) with polymeric isocyanate according to weight Than 1:(1-1.8) carry out proportioning, in casting machine, carry out mix and blend 5-10s obtain fluid mix, then by described liquid Compound is cast between inner panel (1) and outside plate (3), and fluid mix foams voluntarily and solidifies viscous with inner panel (1) and outside plate (3) Knot, forms the cast polyurethane sandwich color steel warming plate of hard polyurethane foam thermal insulation clamp sandwich layer (2).
The technique scheme of the present invention compared with prior art, has the advantage that
1, the rigid foam material of the use of patent of the present invention does not contains low boiling hydrocarbon compound fluorochlorohydrocarbon and HCFC class Compound, with Water blown, does not damages the ozone layer, does not produce greenhouse effect, environmental protection, and this material have employed inorganic miscellaneous when preparing simultaneously The melmac polyhydric alcohol changed, the introducing of inorganic hybridization element improves fire resistance, with the resin-phase before non-hydridization Ratio, resistance to elevated temperatures improves more than 50 DEG C, and fire resistance improves at least 20%, while ensureing physical property, anti-flammability Can be excellent, its oxygen index (OI) is more than 30%, meets GB 8624-2012 standard B1 level requirement.
2, Water blown B1 level flame melamine polyurethane composition polyethers is carried out by the low viscosity phosphate ester that utilizes of the present invention Effective dilution, overcomes water-blown polyurethane combined polyether viscosity too big, poor fluidity, and foaming is uneven and causes abscess thick The defects such as greatly, heat conductivity is bigger than normal, and foams embrittlement, intensity are low.The phosphorus source of phosphorus-nitrogen flame-retardant system is provided simultaneously, improves complete The fire resistance of Water blown polyurethane with melamine foamed materials.
3, the present invention utilizes low viscosity phosphate ester, has been effectively improved full water foamed B1 level flame melamine polyurethane group Close the viscosity of polyethers so that the full water foamed B1 level flame melamine polyurethane rigid foam material of the present invention can spray, permissible With casting machine cast, high pressure panel machine molding can be used, make insulation material.
4, the cast polyurethane sandwich color steel warming plate that patent of the present invention manufactures, it is not necessary to use expensive high fire-retardance Phosphate flame retardant, makes the reduction greatly of foam cost, reduces more than 30%, and economy is more reasonable.
5, the cast polyurethane sandwich color steel warming plate of the present invention compare with like product have obvious technical advantage and Economic advantages, provide environmental protection for building energy conservation, B1 level is fire-retardant, invent waterproof integrated insulation material.Can building field, It is widely used in the fields such as petrochemical industry, freezer cold insulation, great economic benefit will be produced, complete country to perform simultaneously Montreal Agreement plan, reduces atmospheric warming effect, and protection atmospheric ozone layer has huge social benefit.
Accompanying drawing explanation
The cross section structure schematic diagram of the cast polyurethane sandwich color steel warming plate of Fig. 1 present invention
In figure, 1, inner panel, 2, hard polyurethane foam thermal insulation clamp sandwich layer, 3, outside plate
Detailed description of the invention
Describe the present invention in detail below in conjunction with specific embodiment, but the invention is not limited in specific embodiment.
Embodiment 1
Cast polyurethane sandwich color steel warming plate, including inner panel 1 and outside plate 3, is poly-ammonia between described inner panel 1 and outside plate 3 Ester hard bubbles thermal insulation clamp sandwich layer 2, and described hard polyurethane foam thermal insulation clamp sandwich layer 2 is watered by inorganic hybridization polyurethane with melamine rigid foam material Note is formed；
Inorganic hybridization polyurethane with melamine rigid foam material by inorganic hybridization polyurethane with melamine combined polyether be polymerized Isocyanates foaming is made；
Inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula is as follows:
Inner panel 1 and outside plate 3 are color steel.
The thickness of hard polyurethane foam thermal insulation clamp sandwich layer is 0.5cm.
Hard polyurethane foam thermal insulation clamp sandwich layer 2 and inner panel 1, the combination of outside plate 3 are and directly solidify bonding, and cohesive force is 105Kpa。
Emulsifying agent is the silicone oil that hard bubbles.
Composite catalyst is potassium acetate and five methyl diethylentriamine.
Fire retardant is phosphate ester, and phosphate ester is tricresyl phosphate (1-chloro-2-propyl group) ester, and the viscosity of phosphate ester is 290Pa s.
Inorganic hybridization melmac polyhydric alcohol is specially bora melmac propylene glycol, its molecular structural formula And preparation method is as follows:
Proportioning raw materials:
(1) etherification reaction
Hexakis(hydroxymethyl)melamine and methanol being added in reactor according to the above ratio, adding acid for adjusting pH is 2.5, at 35 DEG C Under conditions of, mixing speed is 60 revs/min, and insulation 120min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralizes
Stirring under the conditions of rotating speed 40 revs/min, adding alkali regulation pH is 8.0, and this alkali N-process keeps temperature less than 50 ℃；
(3) hydridization reaction
In reactor, add four water eight sodium borate and water, be warmed up to 100 DEG C of reactions 2 hours, under conditions of 80 DEG C, often Pressure steam methanol, under conditions of 100 DEG C, under the conditions of vacuum is 0.090MPa, steam water, to water content reach 0.5% with Under；
(4) cold filtration
It is cooled to 60 DEG C, adds 2% super-cell, filter out salt with filter, obtain bora etherified melamine Polyimide resin；
(5) ether exchange reaction
Add propylene glycol, and hydrochloric acid, at 100 DEG C, carry out ether exchange reaction, under normal pressure, constantly steam the methanol of generation, Extremely measuring the methanol quality steamed and reach theoretical amount, ether has exchanged；
(6) methanol of distillation removing residual
Under conditions of vacuum 0.090MPa, temperature 95 DEG C, steam the methanol of remaining, be cooled to room temperature, i.e. obtain boron Hydridization melmac propylene glycol, yield 99.0%.
The manufacture forming method of above-mentioned cast polyurethane sandwich color steel warming plate, it is characterised in that: include walking in detail below Rapid:
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components being added separately in mixing kettle, room temperature stirs Mix dispersion 2 hours, filter out trace mechanical admixture, obtain inorganic hybridization polyurethane with melamine combined polyether；
(2) moulding by casting
By the inorganic hybridization polyurethane with melamine combined polyether that obtains in step (1) with polymeric isocyanate according to weight Carry out proportioning than 1:1, in casting machine, carry out mix and blend 5s obtain fluid mix, then described fluid mix is poured into a mould Between inner panel 1 and outside plate 3, fluid mix foams voluntarily and solidifies bonding with inner panel 1 and outside plate 3, forms hard polyurethane foam The cast polyurethane sandwich color steel warming plate of thermal insulation clamp sandwich layer 2.
Can carry out other operations after 10 minutes, construction is unaffected, by this sandwich color steel warming plate at 15 DEG C of bars continuously Under part, placing 48 hours, its intensity can reach 2Mpa.
Embodiment 2
Cast polyurethane sandwich color steel warming plate, including inner panel 1 and outside plate 3, is poly-ammonia between described inner panel 1 and outside plate 3 Ester hard bubbles thermal insulation clamp sandwich layer 2, and described hard polyurethane foam thermal insulation clamp sandwich layer 2 is watered by inorganic hybridization polyurethane with melamine rigid foam material Note is formed；
Inorganic hybridization polyurethane with melamine rigid foam material by inorganic hybridization polyurethane with melamine combined polyether be polymerized Isocyanates foaming is made；
Inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula is as follows:
Inner panel 1 and outside plate 3 are color steel.
The thickness of hard polyurethane foam thermal insulation clamp sandwich layer (2) is 15cm.
Hard polyurethane foam thermal insulation clamp sandwich layer (2) and inner panel (1), the combination of outside plate (3) are and directly solidify bonding, cohesive force For 120Kpa.
Emulsifying agent is the silicone oil that hard bubbles.
Composite catalyst be five methyl diethylentriamine, 1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine, trimethyl- N-2 hydroxypropyl caproic acid and dibutyl tin laurate.
Fire retardant is phosphate ester, and phosphate ester is tricresyl phosphate (2,3-bis-chloropropyl) ester, and the viscosity of phosphate ester is 285Pa s.
Inorganic hybridization melmac polyhydric alcohol is specially molybda melmac glycerol
Molecular structural formula:
Proportioning raw materials:
(1) etherification reaction
Hexakis(hydroxymethyl)melamine and methanol being added in reactor according to the above ratio, adding nitre acid for adjusting pH is 5.0,50 Under conditions of DEG C, mixing speed is 70 revs/min, and insulation 100min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralizes
Stirring under the conditions of rotating speed 70 revs/min, adding alkali regulation pH is 8.6, and this alkali N-process keeps temperature less than 50 ℃；
(3) hydridization reaction
Adding sodium molybdate and water in reactor, be warmed up to 105 DEG C and react 1.5 hours, under conditions of 90 DEG C, normal pressure steams Go out methanol, under conditions of 105 DEG C, under the conditions of vacuum is 0.095MPa, steams water, reaches less than 0.5% to water content；
(4) cold filtration
It is cooled to 70 DEG C, adds 2.5% super-cell, filter out salt with filter, obtain molybdaization etherificate trimerization Melamine resin；
(5) ether exchange reaction
Add glycerol, and nitric acid, at 105 DEG C, carry out ether exchange reaction, under normal pressure, constantly steam the methanol of generation, Extremely measuring the methanol quality steamed and reach theoretical amount, ether has exchanged；
(6) methanol of distillation removing residual
Under conditions of vacuum 0.1MPa, temperature 105 DEG C, steam the methanol of remaining, be cooled to room temperature, i.e. obtain inorganic Hydridization melmac polyhydric alcohol, yield 98.0%.
The manufacture forming method of above-mentioned cast polyurethane sandwich color steel warming plate, it is characterised in that: include walking in detail below Rapid:
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components being added separately in mixing kettle, room temperature stirs Mix dispersion 4 hours, filter out trace mechanical admixture, obtain inorganic hybridization polyurethane with melamine combined polyether；
(2) moulding by casting
By the inorganic hybridization polyurethane with melamine combined polyether that obtains in step (1) with polymeric isocyanate according to weight Carry out proportioning than 1:1.8, in casting machine, carry out mix and blend 10s obtain fluid mix, then by described fluid mix Being cast between inner panel 1 and outside plate 3, fluid mix foams voluntarily and solidifies bonding with inner panel 1 and outside plate 3, forms polyurethane Hard bubble the cast polyurethane sandwich color steel warming plate of thermal insulation clamp sandwich layer 2.
Can carry out other operations after 10 minutes, construction is unaffected, by this sandwich color steel warming plate at 40 DEG C of bars continuously Under part, placing 24 hours, its intensity can reach 1Mpa.
Embodiment 3
Cast polyurethane sandwich color steel warming plate, including inner panel 1 and outside plate 3, is characterized in that: described inner panel 1 and outside plate 3 it Between be hard polyurethane foam thermal insulation clamp sandwich layer 2, described hard polyurethane foam thermal insulation clamp sandwich layer 2 is hard by inorganic hybridization polyurethane with melamine Foam material cast is formed；
Inorganic hybridization polyurethane with melamine rigid foam material by inorganic hybridization polyurethane with melamine combined polyether be polymerized Isocyanates foaming is made；
Described inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula is as follows:
Inner panel 1 and outside plate 3 are color steel.
The thickness of hard polyurethane foam thermal insulation clamp sandwich layer 2 is 25cm.
Hard polyurethane foam thermal insulation clamp sandwich layer 2 and inner panel 1, the combination of outside plate 3 are and directly solidify bonding, and cohesive force is 135Kpa。
Emulsifying agent is the silicone oil that hard bubbles.
Composite catalyst is 1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine, triethylenediamine and N, N-dimethyl benzene Amine.
Fire retardant is phosphate ester, and phosphate ester is tricresyl phosphate (1-chloro-2-propyl group) ester and tricresyl phosphate (2,3-bis-chloropropyl) ester, The viscosity of phosphate ester is 269Pa s.
Inorganic hybridization polyhydric alcohol etherificate melmac is specially stilba diethylene glycol etherificate melmac, its Molecular structural formula and preparation method are as follows:
Molecular structural formula:
Proportioning raw materials:
(1) etherification reaction
Hexakis(hydroxymethyl)melamine and diethylene glycol being added in reactor according to the above ratio, adding acid for adjusting pH is 5.5, Under conditions of 65 DEG C, mixing speed is 80 revs/min, and insulation 30min carries out etherification reaction, obtains diethylene glycol etherificate melamine Polyimide resin；
(2) alkali neutralizes
Being stirred under the conditions of rotating speed 80 revs/min, adding alkali regulation pH is 9.0, and this alkali N-process keeps temperature low In 50 DEG C；
(3) hydridization reaction
Adding antimony oxide and water in reactor, be warmed up to 110 DEG C and react 0.5 hour, hydridization has been reacted；
(4) polyhydric alcohol of distillation removing residual
Under conditions of vacuum 0.1MPa, temperature 100 DEG C, steam the diethylene glycol of the remaining added in step (1)；
(5) cold filtration
It is cooled to 80 DEG C, adds 2.5% super-cell, filter out salt with filter, obtain stilba diethylene glycol Etherified melamine polyimide resin, yield 98.5%.
The manufacture forming method of above-mentioned cast polyurethane sandwich color steel warming plate, it is characterised in that: include walking in detail below Rapid:
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components being added separately in mixing kettle, room temperature stirs Mix dispersion 3 hours, filter out trace mechanical admixture, obtain inorganic hybridization polyurethane with melamine combined polyether；
(2) moulding by casting
By the inorganic hybridization polyurethane with melamine combined polyether that obtains in step (1) with polymeric isocyanate according to weight Carry out proportioning than 1:1.6, in casting machine, carry out mix and blend 9s obtain fluid mix, then described fluid mix is watered Noting between inner panel 1 and outside plate 3, fluid mix foams voluntarily and solidifies bonding with inner panel 1 and outside plate 3, forms rigid polyurethane The cast polyurethane sandwich color steel warming plate of bubble thermal insulation clamp sandwich layer 2.
Can carry out other operations after 10 minutes, construction is unaffected, by this sandwich color steel warming plate at 28 DEG C of bars continuously Under part, placing 29 hours, its intensity can reach 1.2Mpa.
Embodiment 4
Cast polyurethane sandwich color steel warming plate, including inner panel 1 and outside plate 3, is characterized in that: described inner panel 1 and outside plate 3 it Between be hard polyurethane foam thermal insulation clamp sandwich layer 2, described hard polyurethane foam thermal insulation clamp sandwich layer 2 is hard by inorganic hybridization polyurethane with melamine Foam material cast is formed；
Inorganic hybridization polyurethane with melamine rigid foam material by inorganic hybridization polyurethane with melamine combined polyether be polymerized Isocyanates foaming is made；
Inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula is as follows:
Inner panel 1 and outside plate 3 are color steel.
The thickness of hard polyurethane foam thermal insulation clamp sandwich layer 2 is 37cm.
Hard polyurethane foam thermal insulation clamp sandwich layer 2 and inner panel 1, the combination of outside plate 3 are and directly solidify bonding, and cohesive force is 136Kpa。
Emulsifying agent is the silicone oil that hard bubbles.
Composite catalyst is 1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine, trimethyl-N-2 hydroxypropyl caproic acid, Sanya Ethyldiamine, N, accelerine and dibutyl tin laurate
Fire retardant is phosphate ester, and phosphate ester is tricresyl phosphate (2,3-bis-chloropropyl) ester, and the viscosity of phosphate ester is 280Pa s.
Inorganic hybridization melmac polyhydric alcohol is specially bora melmac tetramethylolmethane, its molecular structure As follows with preparation method:
Molecular structural formula:
Proportioning raw materials:
(1) etherification reaction
Hexakis(hydroxymethyl)melamine and methanol being added in reactor according to the above ratio, salt adding acid for adjusting pH is 3.5,55 Under conditions of DEG C, mixing speed is 70 revs/min, and insulation 80min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralizes
Stirring under the conditions of rotating speed 60 revs/min, adding alkali regulation pH is 8.5, and this alkali N-process keeps temperature less than 50 ℃；
(3) hydridization reaction
In reactor, add inorganic hybridization compound and water, be warmed up to 105 DEG C and react 1 hour, under conditions of 90 DEG C, Normal pressure steams methanol, under conditions of 100 DEG C, steams water, reach 0.5% to water content under the conditions of vacuum is 0.090MPa Below；
(4) cold filtration
It is cooled to 70 DEG C, adds 2% super-cell, filter out salt with filter, obtain bora etherified melamine Polyimide resin；
(5) ether exchange reaction
Add tetramethylolmethane, and hydrochloric acid be at 105 DEG C, carries out ether exchange reaction, constantly steams the methanol of generation under normal pressure, Extremely measuring the methanol quality steamed and reach theoretical amount, ether has exchanged；
(6) methanol of distillation removing residual
Under conditions of vacuum 0.090MPa, temperature 100 DEG C, steam the methanol of remaining, be cooled to room temperature, i.e. obtain nothing Machine hydridization melmac polyhydric alcohol, yield 98.0%.
The manufacture forming method of above-mentioned cast polyurethane sandwich color steel warming plate, it is characterised in that: include walking in detail below Rapid:
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components being added separately in mixing kettle, room temperature stirs Mix dispersion 3 hours, filter out trace mechanical admixture, obtain inorganic hybridization polyurethane with melamine combined polyether；
(2) moulding by casting
By the inorganic hybridization polyurethane with melamine combined polyether that obtains in step (1) with polymeric isocyanate according to weight Carry out proportioning than 1:1.4, in casting machine, carry out mix and blend 8s obtain fluid mix, then described fluid mix is watered Noting between inner panel 1 and outside plate 3, fluid mix foams voluntarily and solidifies bonding with inner panel 1 and outside plate 3, forms rigid polyurethane The cast polyurethane sandwich color steel warming plate of bubble thermal insulation clamp sandwich layer 2.
Can carry out other operations after 10 minutes, construction is unaffected, by this sandwich color steel warming plate at 25 DEG C of bars continuously Under part, placing 36 hours, its intensity can reach 1.5Mpa.
Embodiment 5
Cast polyurethane sandwich color steel warming plate, including inner panel 1 and outside plate 3, is characterized in that: described inner panel 1 and outside plate 3 it Between be hard polyurethane foam thermal insulation clamp sandwich layer 2, described hard polyurethane foam thermal insulation clamp sandwich layer 2 is hard by inorganic hybridization polyurethane with melamine Foam material cast is formed；
Inorganic hybridization polyurethane with melamine rigid foam material by inorganic hybridization polyurethane with melamine combined polyether be polymerized Isocyanates foaming is made；
Inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula is as follows:
Inner panel 1 and outside plate 3 are color steel.
The thickness of hard polyurethane foam thermal insulation clamp sandwich layer (2) is 46cm.
Hard polyurethane foam thermal insulation clamp sandwich layer (2) and inner panel (1), the combination of outside plate (3) are and directly solidify bonding, cohesive force For 157Kpa.
Emulsifying agent is the silicone oil that hard bubbles.
Composite catalyst is potassium acetate, trimethyl-N-2 hydroxypropyl caproic acid, triethylenediamine and N, accelerine.
Fire retardant is phosphate ester, and phosphate ester is tricresyl phosphate (1-chloro-2-propyl group) ester and tricresyl phosphate (2,3-bis-chloropropyl) ester, The viscosity of phosphate ester is 289Pa s.
Inorganic hybridization polyhydric alcohol etherificate melmac is specially stilba diethylene glycol etherificate melmac, its Molecular structure and preparation method are as follows:
Molecular structural formula:
Proportioning raw materials:
(1) etherification reaction
Hexakis(hydroxymethyl)melamine and diethylene glycol being added in reactor according to the above ratio, adding acid for adjusting pH is 5.5, Under conditions of 65 DEG C, mixing speed is 80 revs/min, and insulation 30min carries out etherification reaction, obtains diethylene glycol etherificate melamine Polyimide resin；
(2) alkali neutralizes
Being stirred under the conditions of rotating speed 80 revs/min, adding alkali regulation pH is 9.0, and this alkali N-process keeps temperature low In 50 DEG C；
(3) hydridization reaction
Adding antimony oxide and water in reactor, be warmed up to 110 DEG C and react 0.5 hour, hydridization has been reacted；
(4) polyhydric alcohol of distillation removing residual
Under conditions of vacuum 0.1MPa, temperature 100 DEG C, steam the diethylene glycol of the remaining added in step (1)；
(5) cold filtration
It is cooled to 80 DEG C, adds 2.5% super-cell, filter out salt with filter, obtain stilba diethylene glycol Etherified melamine polyimide resin, yield 98.5%.
The manufacture forming method of above-mentioned cast polyurethane sandwich color steel warming plate, it is characterised in that: include walking in detail below Rapid:
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components being added separately in mixing kettle, room temperature stirs Mix dispersion 3.5 hours, filter out trace mechanical admixture, obtain inorganic hybridization polyurethane with melamine combined polyether；
(2) moulding by casting
By the inorganic hybridization polyurethane with melamine combined polyether that obtains in step (1) with polymeric isocyanate according to weight Carry out proportioning than 1:1.3, in casting machine, carry out mix and blend 7s obtain fluid mix, then described fluid mix is watered Noting between inner panel 1 and outside plate 3, fluid mix foams voluntarily and solidifies bonding with inner panel 1 and outside plate 3, forms rigid polyurethane The cast polyurethane sandwich color steel warming plate of bubble thermal insulation clamp sandwich layer 2.
Can carry out other operations after 10 minutes, construction is unaffected, by this sandwich color steel warming plate at 29 DEG C of bars continuously Under part, placing 39 hours, its intensity can reach 1.8Mpa.
Embodiment 6
Cast polyurethane sandwich color steel warming plate, including inner panel 1 and outside plate 3, is characterized in that: described inner panel 1 and outside plate 3 it Between be hard polyurethane foam thermal insulation clamp sandwich layer 2, described hard polyurethane foam thermal insulation clamp sandwich layer 2 is hard by inorganic hybridization polyurethane with melamine Foam material cast is formed；
Inorganic hybridization polyurethane with melamine rigid foam material by inorganic hybridization polyurethane with melamine combined polyether be polymerized Isocyanates foaming is made；
Described inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula is as follows:
Inner panel 1 and outside plate 3 are color steel.
The thickness of hard polyurethane foam thermal insulation clamp sandwich layer 2 is 50cm.
Hard polyurethane foam thermal insulation clamp sandwich layer 2 and inner panel 1, the combination of outside plate 3 are and directly solidify bonding, and cohesive force is 165Kpa。
Emulsifying agent is the silicone oil that hard bubbles.
Composite catalyst is potassium acetate, trimethyl-N-2 hydroxypropyl caproic acid and triethylenediamine.
Fire retardant is phosphate ester, and phosphate ester is tricresyl phosphate (1-chloro-2-propyl group) ester, and the viscosity of phosphate ester is 276Pa s.
Inorganic hybridization polyhydric alcohol etherificate melmac is specially
The preparation of molybda glycerol etherified melamine polyimide resin
Molecular structural formula:
Proportioning raw materials:
(1) etherification reaction
Hexakis(hydroxymethyl)melamine and glycerol being added in reactor according to the above ratio, adding acid for adjusting pH is 4.5,40 Under conditions of DEG C, mixing speed is 65 revs/min, and insulation 90min carries out etherification reaction, obtains glycerol etherified melamine amine tree Fat；
(2) alkali neutralizes
Being stirred under the conditions of rotating speed 70 revs/min, adding alkali regulation pH is 8.5, and this alkali N-process keeps temperature low In 50 DEG C；
(3) hydridization reaction
Adding sodium molybdate and water in reactor, be warmed up to 105 DEG C and react 1.5 hours, hydridization has been reacted；
(4) polyhydric alcohol of distillation removing residual
Under conditions of vacuum 0.1MPa, temperature 120 DEG C, steam the glycerol of the remaining added in step (1)；
(5) cold filtration
It is cooled to 75 DEG C, adds 2% super-cell, filter out salt with filter, obtain molybda glycerol etherificate Melmac, yield 98.2%.
The manufacture forming method of above-mentioned cast polyurethane sandwich color steel warming plate, it is characterised in that: include walking in detail below Rapid:
(1) combined polyether is prepared
Above-mentioned inorganic hybridization polyurethane with melamine combined polyether formula components being added separately in mixing kettle, room temperature stirs Mix dispersion 2.5 hours, filter out trace mechanical admixture, obtain inorganic hybridization polyurethane with melamine combined polyether；
(2) moulding by casting
By the inorganic hybridization polyurethane with melamine combined polyether that obtains in step (1) with polymeric isocyanate according to weight Carry out proportioning than 1:1.4, in casting machine, carry out mix and blend 6s obtain fluid mix, then described fluid mix is watered Noting between inner panel 1 and outside plate 3, fluid mix foams voluntarily and solidifies bonding with inner panel 1 and outside plate 3, forms rigid polyurethane The cast polyurethane sandwich color steel warming plate of bubble thermal insulation clamp sandwich layer 2.
Can carry out other operations after 10 minutes, construction is unaffected, by this sandwich color steel warming plate at 35 DEG C of bars continuously Under part, placing 42 hours, its intensity can reach 1.9Mpa.

Claims (10)

1. cast polyurethane sandwich color steel warming plate, including inner panel (1) and outside plate (3), is characterized in that: described inner panel (1) and outer Being hard polyurethane foam thermal insulation clamp sandwich layer (2) between plate (3), described hard polyurethane foam thermal insulation clamp sandwich layer (2) is by inorganic hybridization trimerization The cast of cyanamide polyurethane rigid foam material is formed；
Described inorganic hybridization polyurethane with melamine rigid foam material by inorganic hybridization polyurethane with melamine combined polyether be polymerized Isocyanates foaming is made；
Described inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula is as follows:
Inorganic hybridization melmac polyhydric alcohol
Or
Described inorganic hybridization polyurethane with melamine combined polyether, by ratio of weight and the number of copies, formula is as follows:
Inorganic hybridization melmac polyhydric alcohol
2. cast polyurethane sandwich color steel warming plate as claimed in claim 1, it is characterised in that: described inner panel (1) and outside plate (3) being sheet metal, described sheet metal is color steel.
3. cast polyurethane sandwich color steel warming plate as claimed in claim 1, it is characterised in that: described hard polyurethane foam is incubated The thickness of laminboard layer (2) is 0.5-50cm.
4. cast polyurethane sandwich color steel warming plate as claimed in claim 1, it is characterised in that: described hard polyurethane foam is incubated Laminboard layer (2) and inner panel (1), the combination of outside plate (3) are and directly solidify bonding, and cohesive force is more than 100Kpa.
5. cast polyurethane sandwich color steel warming plate as claimed in claim 1, it is characterised in that: described emulsifying agent is silicone oil, Described silicone oil is the silicone oil that hard bubbles.
6. cast polyurethane sandwich color steel warming plate as claimed in claim 1, it is characterised in that: described composite catalyst is vinegar Acid potassium, five methyl diethylentriamine, 1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine, trimethyl-N-2 hydroxypropyl caproic acid, Two or more in triethylenediamine, N, accelerine or dibutyl tin laurate.
7. cast polyurethane sandwich color steel warming plate as claimed in claim 1, it is characterised in that: described fire retardant is phosphoric acid Ester, described phosphate ester is one or both in tricresyl phosphate (1-chloro-2-propyl group) ester, tricresyl phosphate (2,3-bis-chloropropyl) ester, institute State the viscosity of phosphate ester less than 300Pa s.
8. cast polyurethane sandwich color steel warming plate as claimed in claim 1, it is characterised in that: described inorganic hybridization trimerization Melamine resin polyol molecule structure is as follows:
X in described molecular structure is inorganic hybridization element, including the one in B or Sb；
R in described molecular structure is-(CH2)nOH or-(CH2)mO(CH2)mOH or
-(OCH2CH2CH2CH3)kOH or-O (CH2)pCH(OH)CH2OH wherein 2≤n≤6,2≤m≤6,2≤p≤6,2≤k≤ 41。
9. cast polyurethane sandwich color steel warming plate as claimed in claim 1, it is characterised in that: described inorganic hybridization is polynary Etherified melmac molecular structure is as follows:
X in described molecular structure is inorganic hybridization element, including the one in B or Sb；
R in described molecular structure is-(CH2)nOH or-(CH2)mO(CH2)mOH or
-(OCH2CH2CH2CH3)kOH or-O (CH2)PCH(OH)CH2OH wherein 2≤n≤6,2≤m≤6,2≤p≤6,2≤k≤ 41。
10. the manufacture forming method of cast polyurethane sandwich color steel warming plate as claimed in claim 1, it is characterised in that: bag Include step in detail below:
(1) combined polyether is prepared
Inorganic hybridization polyurethane with melamine combined polyether formula components in claim 1 is added separately in mixing kettle, Stirring at normal temperature is disperseed 2-4 hour, filters out trace mechanical admixture, obtains inorganic hybridization polyurethane with melamine combined polyether；
(2) moulding by casting
By the inorganic hybridization polyurethane with melamine combined polyether that obtains in step (1) with polymeric isocyanate according to weight ratio 1: (1-1.8) carry out proportioning, in casting machine, carry out mix and blend 5-10s obtain fluid mix, then by described liquid mixing Material is cast between inner panel (1) and outside plate (3), and fluid mix foams voluntarily and solidifies bonding with inner panel (1) and outside plate (3), Form the cast polyurethane sandwich color steel warming plate of hard polyurethane foam thermal insulation clamp sandwich layer (2).
CN201610627253.0A 2016-08-01 2016-08-01 Cast polyurethane sandwich color steel insulation board and its it is manufactured method Active CN106193437B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107829521A (en) * 2017-11-14 2018-03-23 安徽艾米伦特建材科技有限公司 Broomcorn straw polyurethane/rock wool composite partition wall plate and preparation method thereof
CN107938932A (en) * 2017-11-14 2018-04-20 安徽艾米伦特建材科技有限公司 Maize straw polyurethane/rock wool composite partition wall plate and preparation method thereof
CN109749037A (en) * 2018-11-19 2019-05-14 扬州恒丰塑胶有限责任公司 A kind of high resistant combustible polyether glycol, hard polyurethane foam and its preparation method and application

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CN102690661A (en) * 2012-06-07 2012-09-26 常州大学 Hybrid fire retardant and preparing method thereof
CN104262567A (en) * 2014-09-09 2015-01-07 上海应用技术学院 Flame-retardant polyurethane rigid foam taking melamine as basic characteristic and preparation method of flame-retardant polyurethane rigid foam
CN104987484A (en) * 2015-05-29 2015-10-21 张家港迪蒙德节能科技有限公司 Inorganic material hybrid hard melamine polyurethane foam heat insulation material, preparation method thereof and combined polyether used therein

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US20060270747A1 (en) * 2005-05-05 2006-11-30 William Griggs Prime foam containing vegetable oil polyol
CN102295616A (en) * 2011-05-18 2011-12-28 杨彦威 Amino resin having polyhydroxy structure, and preparation method thereof
CN102690661A (en) * 2012-06-07 2012-09-26 常州大学 Hybrid fire retardant and preparing method thereof
CN104262567A (en) * 2014-09-09 2015-01-07 上海应用技术学院 Flame-retardant polyurethane rigid foam taking melamine as basic characteristic and preparation method of flame-retardant polyurethane rigid foam
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107829521A (en) * 2017-11-14 2018-03-23 安徽艾米伦特建材科技有限公司 Broomcorn straw polyurethane/rock wool composite partition wall plate and preparation method thereof
CN107938932A (en) * 2017-11-14 2018-04-20 安徽艾米伦特建材科技有限公司 Maize straw polyurethane/rock wool composite partition wall plate and preparation method thereof
CN109749037A (en) * 2018-11-19 2019-05-14 扬州恒丰塑胶有限责任公司 A kind of high resistant combustible polyether glycol, hard polyurethane foam and its preparation method and application

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