CN106589912A - High-hardness heatproof anti-corrosion polyurethane plate and preparation method thereof - Google Patents
High-hardness heatproof anti-corrosion polyurethane plate and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
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- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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- 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
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- 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
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
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- C08K2201/011—Nanostructured additives
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a high-hardness heatproof anti-corrosion polyurethane plate. The high-hardness heatproof anti-corrosion polyurethane plate is prepared from the following raw materials of diisocyanate, polyester polyol, hydroxyl-terminated polybutadiene, polyethylene glycol terephthalate, nano silica, organosilicone, nano titania, a modification additive, modified graphene oxide, sulphur, dicyandiamide, zinc borate, a silane coupling agent KH-570, an antioxidant, a releasing agent, a curing agent, a cross-linking agent, a foaming agent and copper sheet. The invention also provides a preparation method of the high-hardness heatproof anti-corrosion polyurethane plate. The prepared high-hardness heatproof anti-corrosion polyurethane plate is high in hardness and good in heat-resisting and anti-corrosion properties.
Description
Technical field
The present invention relates to polyurethane material field, more particularly to a kind of high rigidity heat-resistant anticorrosive polyurethane sheet and its preparation side
Method.
Background technology
Polyurethane is a kind of high molecular synthetic material of function admirable, not only the elasticity with rubber but also has had the hardness of plastics,
But also with good mechanical performance, anti-wear performance and rebound performance.Polyurethane sheet is referred to be made up completely of PU, or by PU
The polyurethane laminboard being compounded to form with color steel, is mainly used in industry, civil buildings outer heat preservation system, and having become PU at present makes
Use widest product system.
The hardness of polyurethane sheet of the prior art, demand when heat-resisting and antiseptic property cannot meet actually used, because
Demand when this needs a kind of high rigidity heat-resistant anticorrosive polyurethane sheet of design badly to meet actually used.
The content of the invention
To solve technical problem present in background technology, the present invention propose a kind of high rigidity heat-resistant anticorrosive polyurethane sheet and
Its preparation method, the polyurethane sheet hardness for preparing is high, and heat-resistant anticorrosive performance is strong.
A kind of high rigidity heat-resistant anticorrosive polyurethane sheet proposed by the present invention, its raw material includes by weight：Diisocyanate
80-120 parts, PEPA 10-30 parts, end hydroxy butadiene 4-8 parts, polyethylene terephthalate 3-6 part, nanometer
Silicon dioxide 4-9 parts, organosilicon 4-6 parts, nano titanium oxide 2-4 parts, modified additive 5-15 parts, modified graphene oxide 4-8
Part, sulfur 2-5 parts, dicyandiamide 4-8 parts, Firebrake ZB 3-6 parts, Silane coupling reagent KH-570 1-5 parts, antioxidant 2-8 parts, the demoulding
Agent 1-6 parts, firming agent 2-5 parts, cross-linking agent 3-6 parts, foaming agent 2-6 parts, copper sheet 5-15 parts.
Preferably, modified additive is prepared by following technique：Triple superphosphate is put in calcining furnace and is calcined at 820-920 DEG C
2-5h, cooling is put in the hydrochloric acid solution that mass percent is 4-6% and soaks 1-3h, filters and takes out, and with clear water drying is cleaned,
Crushing obtains material a, then by material a, carbamate, isopropyl acrylate, white carbon, nano zine oxide, toughener, wood
Matter fiber and waterproofing agent mix homogeneously, grinding distribution uniformly obtains material b, then by polypropylene and material b mix homogeneously, heating
To 320-480 DEG C, 12-18min is incubated, is cooled to room temperature, be subsequently adding politef and glass fibre ball milling 12-16min,
Obtain material c；By aluminium oxide and aluminium dihydrogen phosphate mix homogeneously, 68-89 DEG C is heated to, is incubated 10-30min, be subsequently adding season penta
Tetrol triacrylate is stirred to room temperature and obtains material d, and then by material c and material d mix homogeneously, drying, grinding is cooled to
Room temperature obtains modified additive.
Preferably, in the preparation technology of modified additive, triple superphosphate, mass percent are hydrochloric acid solution, the carbamic acid of 4-6%
Ester, isopropyl acrylate, white carbon, nano zine oxide, toughener, wood fibre, waterproofing agent, polypropylene, politef, glass
The weight ratio of glass fiber, aluminium oxide, aluminium dihydrogen phosphate and pentaerythritol triacrylate is 1-3：2-4：3-5：2-6：1-3：1-
2：1.5-2.5：1-3：2-6：3-5：2-4：1-3：2-5：3-5：2-6.
Preferably, modified graphene oxide is prepared by following technique：By graphene oxide and hydrazine hydrate mix homogeneously,
10-12h is stirred in 65-75 DEG C, 1,8- diazabicycloundecenes, bromo diethyl malonate and carboxyl butyronitrile glue is subsequently adding
Newborn mix homogeneously, under 5500-6500r/min rotating speeds 2-4h is stirred, and then heats to 90-100 DEG C, is incubated 0.5-1.5h, so
After pour in aluminum sulfate condense, then deionized water cleaning after, sucking filtration is placed in 45-55 DEG C of baking oven and is dried 1-4h, cooling
Modified graphene oxide is obtained to room temperature.
Preferably, in the preparation technology of modified graphene oxide, graphene oxide, hydrazine hydrate, 1,8- diazabicyclos ten
The weight ratio of one alkene, bromo diethyl malonate, carboxylic acrylonitrile butadiene rubber latex and aluminum sulfate is 5-15：2-5：3-6：1-3：2-5：1-4.
Preferably, its raw material includes by weight：Diisocyanate 85-115 parts, PEPA 15-25 parts, terminal hydroxy group
Polybutadiene 5-7 parts, polyethylene terephthalate 4-5 part, nano silicon 5-8 parts, organosilicon 4.5-5.5 parts, receive
Rice titanium dioxide 2.5-3.5 parts, modified additive 8-12 parts, modified graphene oxide 5-7 parts, sulfur 3-4 parts, dicyandiamide 5-7 parts,
Firebrake ZB 4-5 parts, Silane coupling reagent KH-570 2-4 parts, antioxidant 3-7 parts, releasing agent 2-5 parts, firming agent 3-4 parts, cross-linking agent
4-5 parts, foaming agent 3-5 parts, copper sheet 8-12 parts.
Preferably, its raw material includes by weight：100 parts of diisocyanate, 20 parts of PEPA, terminal hydroxy group polybutadiene
6 parts of alkene, 4.5 parts of polyethylene terephthalate, 6.5 parts of nano silicon, 5 parts of organosilicon, 3 parts of nano titanium oxide,
10 parts of modified additive, 6 parts of modified graphene oxide, 3.5 parts of sulfur, 6 parts of dicyandiamide, 4.5 parts of Firebrake ZB, silane coupler KH-
570 3 parts, 5 parts of antioxidant, 3.5 parts of releasing agent, 3.5 parts of firming agent, 4.5 parts of cross-linking agent, 4 parts of foaming agent, 10 parts of copper sheet.
A kind of preparation method of the high rigidity heat-resistant anticorrosive polyurethane sheet of the present invention, including：Diisocyanate, polyester is more
First alcohol, end hydroxy butadiene, nano silicon, organosilicon, nano titanium oxide, modified additive, modified graphene oxide,
Sulfur, dicyandiamide, Firebrake ZB, Silane coupling reagent KH-570, antioxidant, firming agent, cross-linking agent and foaming agent are sufficiently stirred for, mix
It is even, polyethylene terephthalate is subsequently adding, water mixing is stirring evenly and then adding into, then pour into immediately in mould in 80-
140 DEG C of insulations are compressing, stand 20-40min, are put into 120-140 DEG C of ripening 5-8h in baking oven, add the demoulding after releasing agent to obtain
To plate body, then copper sheet is covered with plate body surface, copper sheet surface-pressure, room temperature stands 4-6h, is cooled to room temperature and obtains high rigidity
Heat-resistant anticorrosive polyurethane sheet.
A kind of high rigidity heat-resistant anticorrosive polyurethane sheet of the present invention, its raw material includes diisocyanate, PEPA, end
Hydroxyl polybutadiene, polyethylene terephthalate, nano silicon, organosilicon, nano titanium oxide, modified additive,
Modified graphene oxide, sulfur, dicyandiamide, Firebrake ZB, Silane coupling reagent KH-570, antioxidant, releasing agent, firming agent, crosslinking
Agent, foaming agent and copper sheet.Wherein with diisocyanate as major ingredient, with PEPA, end hydroxy butadiene, poly- terephthaldehyde
Sour glycol ester, sulfur, dicyandiamide, Firebrake ZB, Silane coupling reagent KH-570, antioxidant, releasing agent, firming agent, cross-linking agent and
Foaming agent is auxiliary agent, with nano silicon, organosilicon, nano titanium oxide, modified additive and modified graphene oxide to fill out
Material, through the cooperation of major ingredient, auxiliary agent and filler, effectively increases the high rigidity heat-resistant anticorrosive performance of the present invention.Wherein add
Nano silicon, organosilicon and nano titanium oxide are realized to nano-silica in the presence of Silane coupling reagent KH-570
Being modified for SiClx, organosilicon and nano titanium oxide, effectively increases the combination of itself and major ingredient, improves polyurethane sheet of the present invention
Hardness, heat-resisting and antiseptic property.Hydrochloric acid solution of the modified additive with triple superphosphate, mass percent as 4-6% that add in filler,
Carbamate, isopropyl acrylate, white carbon, nano zine oxide, toughener, wood fibre, waterproofing agent, polypropylene, poly- four
Fluorothene, glass fibre, aluminium oxide, aluminium dihydrogen phosphate and pentaerythritol triacrylate are raw material, through modified auxiliary agent, fortune
In the preparation process of the polyurethane sheet for using the present invention, in the presence of Silane coupling reagent KH-570, the present invention is effectively increased
The hardness of polyurethane sheet, heat-resistant anticorrosive performance.The modified graphene oxide of addition is with graphene oxide, hydrazine hydrate, 1,8- phenodiazines
Miscellaneous bicyclic hendecene, bromo diethyl malonate, carboxylic acrylonitrile butadiene rubber latex and aluminum sulfate are raw material, with hydrazine hydrate as reducing agent,
In the presence of flocculating agent, by graphene oxide, 1,8- diazabicycloundecenes, bromo diethyl malonate and carboxyl butyronitrile glue
Breast carries out copolyreaction, and the modified graphene oxide for preparing is applied in the preparation of the polyurethane sheet of the present invention, in silane
Modified grafting is realized in the presence of coupling agent kh-570, the hardness of polyurethane sheet of the present invention, heat-resisting and anti-corrosive properties are effectively increased
Energy.The preparation method of the present invention is simple, and the polyurethane sheet hardness for preparing is high, and heat-resistant anticorrosive performance is good.
Specific embodiment
The present invention is described in detail with reference to specific embodiment, it should be appreciated that embodiment is served only for illustrating this
It is bright, rather than for limiting the invention, any modification made on the basis of the present invention, equivalent etc. are at this
In bright protection domain.
In specific embodiment, the weight portion of diisocyanate can for 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105
Part, 110 parts, 115 parts, 120 parts；The weight portion of PEPA can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts；Terminal hydroxy group
The weight portion of polybutadiene can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts；The weight portion of polyethylene terephthalate can be 3
Part, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The weight portion of nano silicon can for 4 parts, 4.5 parts, 5 parts, 5.5
Part, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts；The weight portion of organosilicon can for 4 parts, 4.5 parts, 5 parts, 5.5 parts,
6 parts；The weight portion of nano titanium oxide can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；The weight portion of modified additive can be 5
Part, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts；The weight portion of modified graphene oxide can be
4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts；The weight portion of sulfur can for 2 parts, 2.5 parts, 3 parts,
3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight portion of dicyandiamide can for 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5
Part, 8 parts；The weight portion of Firebrake ZB can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；Silane coupling reagent KH-570
Weight portion can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts；The weight portion of antioxidant can for 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7
Part, 8 parts；The weight portion of releasing agent can for 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts,
6 parts；The weight portion of firming agent can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight portion of cross-linking agent can be with
For 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The weight portion of foaming agent can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；
The weight portion of copper sheet can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts.
Embodiment 1
A kind of high rigidity heat-resistant anticorrosive polyurethane sheet proposed by the present invention, its raw material includes by weight：Diisocyanate
100 parts, 20 parts of PEPA, 6 parts of end hydroxy butadiene, 4.5 parts of polyethylene terephthalate, nano silicon
6.5 parts, 5 parts of organosilicon, 3 parts of nano titanium oxide, 10 parts of modified additive, 6 parts of modified graphene oxide, 3.5 parts of sulfur, double cyanogen
6 parts of amine, 4.5 parts of Firebrake ZB, 3 parts of Silane coupling reagent KH-570,5 parts of antioxidant, 3.5 parts of releasing agent, 3.5 parts of firming agent, crosslinking
4.5 parts of agent, 4 parts of foaming agent, 10 parts of copper sheet.
Modified additive is prepared by following technique：2 parts of triple superphosphate are put in calcining furnace are by weight calcined at 900 DEG C
3.5h, cooling is put in the hydrochloric acid solution that 3 parts of mass percents are 5% and soaks 2h, filters and takes out, and with clear water drying, powder are cleaned
It is broken to obtain material a, then by material a, 4 parts of carbamates, 4 parts of isopropyl acrylates, 2 parts of white carbons, 1.5 parts it is nano oxidized
Zinc, 2 parts of toughener, 2 parts of wood fibres and 4 parts of waterproofing agent mix homogeneously, grinding distribution uniformly obtains material b, then poly- by 4 parts
Propylene and material b mix homogeneously, are heated to 400 DEG C, are incubated 15min, are cooled to room temperature, are subsequently adding 3 parts of politef and 2
Part glass fibre ball milling 14min, obtains material c；By 3.5 parts of aluminium oxidies and 4 parts of aluminium dihydrogen phosphate mix homogeneously, 78.5 are heated to
DEG C, 20min is incubated, it is subsequently adding 4 parts of pentaerythritol triacrylates and stirs to room temperature and obtain material d, then by material c and thing
Material d mix homogeneously, drying, grinding is cooled to room temperature and obtains modified additive.
Modified graphene oxide is prepared by following technique：By weight by 10 parts of graphene oxides and 3.5 parts of hydrations
Hydrazine mix homogeneously, in 70 DEG C 11h is stirred, and is subsequently adding 5.5 parts of 1,8- diazabicycloundecenes, 2 parts of bromomalonic acid diethyls
Ester and 3.5 parts of carboxylic acrylonitrile butadiene rubber latex mix homogeneously, under 6000r/min rotating speeds 3h is stirred, and then heats to 95 DEG C, is incubated 1h,
It is subsequently poured in 2.5 parts of aluminum sulfate and condenses, then after deionized water cleaning, sucking filtration is placed in 50 DEG C of baking oven and is dried 2.5h,
It is cooled to room temperature and obtains modified graphene oxide.
A kind of preparation method of the high rigidity heat-resistant anticorrosive polyurethane sheet of the present invention, including：Diisocyanate, polyester is more
First alcohol, end hydroxy butadiene, nano silicon, organosilicon, nano titanium oxide, modified additive, modified graphene oxide,
Sulfur, dicyandiamide, Firebrake ZB, Silane coupling reagent KH-570, antioxidant, firming agent, cross-linking agent and foaming agent are sufficiently stirred for, mix
It is even, polyethylene terephthalate is subsequently adding, water mixing is stirring evenly and then adding into, then pour into immediately in mould in 110
DEG C insulation is compressing, stands 30min, is put into 130 DEG C of ripening 6.5h in baking oven, adds the demoulding after releasing agent to obtain plate body, connects
And be covered with copper sheet on plate body surface, copper sheet surface-pressure, room temperature stands 5h, is cooled to room temperature and obtains the poly- ammonia of high rigidity heat-resistant anticorrosive
Ester plate.
Embodiment 2
A kind of high rigidity heat-resistant anticorrosive polyurethane sheet proposed by the present invention, its raw material includes by weight：Diisocyanate
80 parts, 30 parts of PEPA, 4 parts of end hydroxy butadiene, 6 parts of polyethylene terephthalate, nano silicon 4
Part, 6 parts of organosilicon, 2 parts of nano titanium oxide, 15 parts of modified additive, 4 parts of modified graphene oxide, 5 parts of sulfur, dicyandiamide 4
Part, 6 parts of Firebrake ZB, 1 part of Silane coupling reagent KH-570,8 parts of antioxidant, 1 part of releasing agent, 5 parts of firming agent, 3 parts of cross-linking agent, foaming
6 parts of agent, 5 parts of copper sheet.
Modified additive is prepared by following technique：1 part of triple superphosphate is put in calcining furnace is by weight calcined at 920 DEG C
2h, cooling is put in the hydrochloric acid solution that 4 parts of mass percents are 4% and soaks 3h, filters and takes out, and with clear water drying is cleaned, and crushes
Obtain material a, then by material a, 3 parts of carbamates, 6 parts of isopropyl acrylates, 1 part of white carbon, 2 parts of nano zine oxides,
1.5 parts of toughener, 3 parts of wood fibres and 2 parts of waterproofing agent mix homogeneously, grinding distribution uniformly obtains material b, then poly- by 5 parts
Propylene and material b mix homogeneously, are heated to 320 DEG C, are incubated 18min, are cooled to room temperature, are subsequently adding 2 parts of politef and 3
Part glass fibre ball milling 12min, obtains material c；By 5 parts of aluminium oxidies and 3 parts of aluminium dihydrogen phosphate mix homogeneously, 89 DEG C are heated to, are protected
Warm 10min, is subsequently adding 6 parts of pentaerythritol triacrylates and stirs to room temperature and obtain material d, then mixes material c and material d
Close uniform, drying, grinding is cooled to room temperature and obtains modified additive.
Modified graphene oxide is prepared by following technique：5 parts of graphene oxides and 5 parts of hydrazine hydrates are mixed by weight
Close uniform, in 65 DEG C 12h are stirred, be subsequently adding 3 parts of 1,8- diazabicycloundecenes, 3 parts of bromo diethyl malonates and 2 parts
Carboxylic acrylonitrile butadiene rubber latex mix homogeneously, under 6500r/min rotating speeds 2h is stirred, and then heats to 100 DEG C, is incubated 0.5h, is then fallen
Enter in 4 parts of aluminum sulfate and condense, then after deionized water cleaning, sucking filtration is placed in 45 DEG C of baking oven and is dried 4h, is cooled to room temperature
Obtain modified graphene oxide.
A kind of preparation method of the high rigidity heat-resistant anticorrosive polyurethane sheet of the present invention, including：Diisocyanate, polyester is more
First alcohol, end hydroxy butadiene, nano silicon, organosilicon, nano titanium oxide, modified additive, modified graphene oxide,
Sulfur, dicyandiamide, Firebrake ZB, Silane coupling reagent KH-570, antioxidant, firming agent, cross-linking agent and foaming agent are sufficiently stirred for, mix
It is even, polyethylene terephthalate is subsequently adding, water mixing is stirring evenly and then adding into, then pour into immediately in mould in 80 DEG C
Insulation is compressing, stands 40min, is put into 120 DEG C of ripening 8h in baking oven, adds the demoulding after releasing agent to obtain plate body, then exists
Plate body surface is covered with copper sheet, and copper sheet surface-pressure, room temperature stands 4h, is cooled to room temperature and obtains high rigidity heat-resistant anticorrosive polyurethane
Plate.
Embodiment 3
A kind of high rigidity heat-resistant anticorrosive polyurethane sheet proposed by the present invention, its raw material includes by weight：Diisocyanate
120 parts, 10 parts of PEPA, 8 parts of end hydroxy butadiene, 3 parts of polyethylene terephthalate, nano silicon 9
Part, 4 parts of organosilicon, 4 parts of nano titanium oxide, 5 parts of modified additive, 8 parts of modified graphene oxide, 2 parts of sulfur, 8 parts of dicyandiamide,
3 parts of Firebrake ZB, 5 parts of Silane coupling reagent KH-570,2 parts of antioxidant, 6 parts of releasing agent, 2 parts of firming agent, 6 parts of cross-linking agent, foaming agent 2
Part, 15 parts of copper sheet.
Modified additive is prepared by following technique：3 parts of triple superphosphate are put in calcining furnace are by weight calcined at 820 DEG C
5h, cooling is put in the hydrochloric acid solution that 2 parts of mass percents are 6% and soaks 1h, filters and takes out, and with clear water drying is cleaned, and crushes
Obtain material a, then by material a, 5 parts of carbamates, 2 parts of isopropyl acrylates, 3 parts of white carbons, 1 part of nano zine oxide,
2.5 parts of toughener, 1 part of wood fibre and 6 parts of waterproofing agent mix homogeneously, grinding distribution uniformly obtains material b, then poly- by 3 parts
Propylene and material b mix homogeneously, are heated to 480 DEG C, are incubated 12min, are cooled to room temperature, are subsequently adding 4 parts of politef and 1
Part glass fibre ball milling 16min, obtains material c；By 2 parts of aluminium oxidies and 5 parts of aluminium dihydrogen phosphate mix homogeneously, 68 DEG C are heated to, are protected
Warm 30min, is subsequently adding 2 parts of pentaerythritol triacrylates and stirs to room temperature and obtain material d, then mixes material c and material d
Close uniform, drying, grinding is cooled to room temperature and obtains modified additive.
Modified graphene oxide is prepared by following technique：By weight by 15 parts of graphene oxides and 2 parts of hydrazine hydrates
Mix homogeneously, in 75 DEG C 10h is stirred, and is subsequently adding 6 parts of 1,8- diazabicycloundecenes, 1 part of bromo diethyl malonate and 5
Part carboxylic acrylonitrile butadiene rubber latex mix homogeneously, under 5500r/min rotating speeds 4h is stirred, and then heats to 90 DEG C, is incubated 1.5h, is then fallen
Enter in 1 part of aluminum sulfate and condense, then after deionized water cleaning, sucking filtration is placed in 55 DEG C of baking oven and is dried 1h, is cooled to room temperature
Obtain modified graphene oxide.
A kind of preparation method of the high rigidity heat-resistant anticorrosive polyurethane sheet of the present invention, including：Diisocyanate, polyester is more
First alcohol, end hydroxy butadiene, nano silicon, organosilicon, nano titanium oxide, modified additive, modified graphene oxide,
Sulfur, dicyandiamide, Firebrake ZB, Silane coupling reagent KH-570, antioxidant, firming agent, cross-linking agent and foaming agent are sufficiently stirred for, mix
It is even, polyethylene terephthalate is subsequently adding, water mixing is stirring evenly and then adding into, then pour into immediately in mould in 140
DEG C insulation is compressing, stands 20min, is put into 140 DEG C of ripening 5h in baking oven, adds the demoulding after releasing agent to obtain plate body, then
Copper sheet is covered with plate body surface, copper sheet surface-pressure, room temperature stands 6h, is cooled to room temperature and obtains high rigidity heat-resistant anticorrosive polyurethane
Plate.
Embodiment 4
A kind of high rigidity heat-resistant anticorrosive polyurethane sheet proposed by the present invention, its raw material includes by weight：Diisocyanate
85 parts, 25 parts of PEPA, 5 parts of end hydroxy butadiene, 5 parts of polyethylene terephthalate, nano silicon 5
Part, 5.5 parts of organosilicon, 2.5 parts of nano titanium oxide, 12 parts of modified additive, 5 parts of modified graphene oxide, 4 parts of sulfur, double cyanogen
5 parts of amine, 5 parts of Firebrake ZB, 2 parts of Silane coupling reagent KH-570,7 parts of antioxidant, 2 parts of releasing agent, 4 parts of firming agent, 4 parts of cross-linking agent,
5 parts of foaming agent, 8 parts of copper sheet.
Modified additive is prepared by following technique：1.5 parts of triple superphosphate are put in calcining furnace are by weight forged at 910 DEG C
3h is burnt, cooling is put in the hydrochloric acid solution that 3.5 parts of mass percents are 4.5% and soaks 2.5h, filter and take out, cleaned with clear water
Drying, crushing obtains material a, then by material a, 3.5 parts of carbamates, 5 parts of isopropyl acrylates, 1.5 parts of white carbons,
1.8 parts of nano zine oxides, 1.8 parts of toughener, 2.5 parts of wood fibres and 3 parts of waterproofing agent mix homogeneously, grinding distribution is uniformly obtained
Material b, then by 4.5 parts of polypropylene and material b mix homogeneously, is heated to 330 DEG C, is incubated 17min, is cooled to room temperature, then
2.5 parts of politef and 2.5 parts of glass fibre ball milling 13min are added, material c is obtained；By 4 parts of aluminium oxidies and 3.5 parts of di(2-ethylhexyl)phosphates
Hydrogen aluminum mix homogeneously, is heated to 88 DEG C, is incubated 15min, is subsequently adding 5 parts of pentaerythritol triacrylates and stirs to room temperature and obtains
Material d, then by material c and material d mix homogeneously, drying, grinding is cooled to room temperature and obtains modified additive.
Modified graphene oxide is prepared by following technique：8 parts of graphene oxides and 4 parts of hydrazine hydrates are mixed by weight
Close uniform, in 68 DEG C 11.5h is stirred, be subsequently adding 4 parts of 1,8- diazabicycloundecenes, 2.5 parts of bromo diethyl malonates
With 3 parts of carboxylic acrylonitrile butadiene rubber latex mix homogeneously, 2.5h is stirred under 6200r/min rotating speeds, then heats to 98 DEG C, be incubated 0.8h,
It is subsequently poured in 3 parts of aluminum sulfate and condenses, then after deionized water cleaning, sucking filtration is placed in 48 DEG C of baking oven and is dried 3h, cooling
Modified graphene oxide is obtained to room temperature.
A kind of preparation method of the high rigidity heat-resistant anticorrosive polyurethane sheet of the present invention, including：Diisocyanate, polyester is more
First alcohol, end hydroxy butadiene, nano silicon, organosilicon, nano titanium oxide, modified additive, modified graphene oxide,
Sulfur, dicyandiamide, Firebrake ZB, Silane coupling reagent KH-570, antioxidant, firming agent, cross-linking agent and foaming agent are sufficiently stirred for, mix
It is even, polyethylene terephthalate is subsequently adding, water mixing is stirring evenly and then adding into, then pour into immediately in mould in 85 DEG C
Insulation is compressing, stands 35min, is put into 125 DEG C of ripening 7h in baking oven, adds the demoulding after releasing agent to obtain plate body, then exists
Plate body surface is covered with copper sheet, and copper sheet surface-pressure, room temperature stands 4.5h, is cooled to room temperature and obtains high rigidity heat-resistant anticorrosive polyurethane
Plate.
Embodiment 5
A kind of high rigidity heat-resistant anticorrosive polyurethane sheet proposed by the present invention, its raw material includes by weight：Diisocyanate
115 parts, 15 parts of PEPA, 7 parts of end hydroxy butadiene, 4 parts of polyethylene terephthalate, nano silicon 8
Part, 4.5 parts of organosilicon, 3.5 parts of nano titanium oxide, 8 parts of modified additive, 7 parts of modified graphene oxide, 3 parts of sulfur, dicyandiamide
7 parts, 4 parts of Firebrake ZB, 4 parts of Silane coupling reagent KH-570,3 parts of antioxidant, 5 parts of releasing agent, 3 parts of firming agent, cross-linking agent 5 part,
3 parts of infusion, 12 parts of copper sheet.
Modified additive is prepared by following technique：2.5 parts of triple superphosphate are put in calcining furnace are by weight forged at 830 DEG C
4h is burnt, cooling is put in the hydrochloric acid solution that 2.5 parts of mass percents are 5.5% and soaks 1.5h, filter and take out, cleaned with clear water
Drying, crushing obtains material a, then by material a, 4.5 parts of carbamates, 3 parts of isopropyl acrylates, 2.5 parts of white carbons,
1.2 parts of nano zine oxides, 2.2 parts of toughener, 1.5 parts of wood fibres and 5 parts of waterproofing agent mix homogeneously, grinding distribution is uniformly obtained
Material b, then by 3.5 parts of polypropylene and material b mix homogeneously, is heated to 470 DEG C, is incubated 13min, is cooled to room temperature, then
3.5 parts of politef and 1.5 parts of glass fibre ball milling 15min are added, material c is obtained；By 3 parts of aluminium oxidies and 4.5 parts of di(2-ethylhexyl)phosphates
Hydrogen aluminum mix homogeneously, is heated to 69 DEG C, is incubated 25min, is subsequently adding 3 parts of pentaerythritol triacrylates and stirs to room temperature and obtains
Material d, then by material c and material d mix homogeneously, drying, grinding is cooled to room temperature and obtains modified additive.
Modified graphene oxide is prepared by following technique：By weight by 12 parts of graphene oxides and 3 parts of hydrazine hydrates
Mix homogeneously, in 72 DEG C 10.5h is stirred, and is subsequently adding 5 parts of 1,8- diazabicycloundecenes, 1.5 parts of bromomalonic acid diethyls
Ester and 4 parts of carboxylic acrylonitrile butadiene rubber latex mix homogeneously, under 5800r/min rotating speeds 3.5h is stirred, and then heats to 92 DEG C, insulation
1.2h, is subsequently poured in 2 parts of aluminum sulfate and condenses, and then after deionized water cleaning, sucking filtration is placed in 52 DEG C of baking oven and is dried
2h, is cooled to room temperature and obtains modified graphene oxide.
A kind of preparation method of the high rigidity heat-resistant anticorrosive polyurethane sheet of the present invention, including：Diisocyanate, polyester is more
First alcohol, end hydroxy butadiene, nano silicon, organosilicon, nano titanium oxide, modified additive, modified graphene oxide,
Sulfur, dicyandiamide, Firebrake ZB, Silane coupling reagent KH-570, antioxidant, firming agent, cross-linking agent and foaming agent are sufficiently stirred for, mix
It is even, polyethylene terephthalate is subsequently adding, water mixing is stirring evenly and then adding into, then pour into immediately in mould in 135
DEG C insulation is compressing, stands 25min, is put into 135 DEG C of ripening 6h in baking oven, adds the demoulding after releasing agent to obtain plate body, then
Copper sheet is covered with plate body surface, copper sheet surface-pressure, room temperature stands 5.5h, is cooled to room temperature and obtains the poly- ammonia of high rigidity heat-resistant anticorrosive
Ester plate.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept equivalent or change in addition, all should be included within the scope of the present invention.
Claims (8)
1. a kind of high rigidity heat-resistant anticorrosive polyurethane sheet, it is characterised in that its raw material includes by weight：Diisocyanate 80-
120 parts, PEPA 10-30 parts, end hydroxy butadiene 4-8 parts, polyethylene terephthalate 3-6 part, nanometer two
Silicon oxide 4-9 parts, organosilicon 4-6 parts, nano titanium oxide 2-4 parts, modified additive 5-15 parts, modified graphene oxide 4-8 parts,
Sulfur 2-5 parts, dicyandiamide 4-8 parts, Firebrake ZB 3-6 parts, Silane coupling reagent KH-570 1-5 parts, antioxidant 2-8 parts, releasing agent 1-
6 parts, firming agent 2-5 parts, cross-linking agent 3-6 parts, foaming agent 2-6 parts, copper sheet 5-15 parts.
2. high rigidity heat-resistant anticorrosive polyurethane sheet according to claim 1, it is characterised in that modified additive presses following technique
It is prepared：Triple superphosphate is put in calcining furnace and calcines 2-5h at 820-920 DEG C, cooled down, be put into mass percent for 4-6%'s
1-3h is soaked in hydrochloric acid solution, is filtered and is taken out, with clear water drying is cleaned, crushing obtains material a, then by material a, carbamic acid
Ester, isopropyl acrylate, white carbon, nano zine oxide, toughener, wood fibre and waterproofing agent mix homogeneously, grinding distribution is equal
It is even to obtain material b, then by polypropylene and material b mix homogeneously, 320-480 DEG C is heated to, 12-18min is incubated, it is cooled to often
Temperature, is subsequently adding politef and glass fibre ball milling 12-16min, obtains material c；Aluminium oxide and aluminium dihydrogen phosphate are mixed
Uniformly, it is heated to 68-89 DEG C, is incubated 10-30min, is subsequently adding pentaerythritol triacrylate and stirs to room temperature and obtain material
D, then by material c and material d mix homogeneously, drying, grinding is cooled to room temperature and obtains modified additive.
3. high rigidity heat-resistant anticorrosive polyurethane sheet according to claim 2, it is characterised in that the preparation technology of modified additive
In, triple superphosphate, mass percent are the hydrochloric acid solution of 4-6%, carbamate, isopropyl acrylate, white carbon, nano oxidized
Zinc, toughener, wood fibre, waterproofing agent, polypropylene, politef, glass fibre, aluminium oxide, aluminium dihydrogen phosphate and season penta
The weight ratio of tetrol triacrylate is 1-3：2-4：3-5：2-6：1-3：1-2：1.5-2.5：1-3：2-6：3-5：2-4：1-3：
2-5：3-5：2-6.
4. the high rigidity heat-resistant anticorrosive polyurethane sheet according to any one of claim 1-3, it is characterised in that modified oxidized stone
Black alkene is prepared by following technique：By graphene oxide and hydrazine hydrate mix homogeneously, 10-12h is stirred in 65-75 DEG C, then
1,8- diazabicycloundecenes, bromo diethyl malonate and carboxylic acrylonitrile butadiene rubber latex mix homogeneously are added, in 5500-6500r/
2-4h is stirred under min rotating speeds, 90-100 DEG C is then heated to, 0.5-1.5h is incubated, is subsequently poured in aluminum sulfate and is condensed, then used
After deionized water cleaning, sucking filtration is placed in 45-55 DEG C of baking oven and is dried 1-4h, is cooled to room temperature and obtains modified graphene oxide.
5. the high rigidity heat-resistant anticorrosive polyurethane sheet according to any one of claim 1-4, it is characterised in that modified oxidized stone
In the preparation technology of black alkene, graphene oxide, hydrazine hydrate, 1,8- diazabicycloundecenes, bromo diethyl malonate, carboxyl
The weight ratio of NBR latex and aluminum sulfate is 5-15：2-5：3-6：1-3：2-5：1-4.
6. the high rigidity heat-resistant anticorrosive polyurethane sheet according to any one of claim 1-5, it is characterised in that its raw material is by weight
Amount part includes：Diisocyanate 85-115 parts, PEPA 15-25 parts, end hydroxy butadiene 5-7 parts, poly- terephthaldehyde
It is sour glycol ester 4-5 parts, nano silicon 5-8 parts, organosilicon 4.5-5.5 parts, nano titanium oxide 2.5-3.5 parts, modified
Auxiliary agent 8-12 parts, modified graphene oxide 5-7 parts, sulfur 3-4 parts, dicyandiamide 5-7 parts, Firebrake ZB 4-5 parts, silane coupler
KH-570 2-4 parts, antioxidant 3-7 parts, releasing agent 2-5 parts, firming agent 3-4 parts, cross-linking agent 4-5 parts, foaming agent 3-5 parts, copper sheet
8-12 parts.
7. the high rigidity heat-resistant anticorrosive polyurethane sheet according to any one of claim 1-6, it is characterised in that its raw material is by weight
Amount part includes：100 parts of diisocyanate, 20 parts of PEPA, 6 parts of end hydroxy butadiene, polyethylene terephthalate
4.5 parts of ester, 6.5 parts of nano silicon, 5 parts of organosilicon, 3 parts of nano titanium oxide, 10 parts of modified additive, modified graphite oxide
6 parts of alkene, 3.5 parts of sulfur, 6 parts of dicyandiamide, 4.5 parts of Firebrake ZB, 3 parts of Silane coupling reagent KH-570,5 parts of antioxidant, releasing agent
3.5 parts, 3.5 parts of firming agent, 4.5 parts of cross-linking agent, 4 parts of foaming agent, 10 parts of copper sheet.
8. a kind of preparation method of the high rigidity heat-resistant anticorrosive polyurethane sheet according to any one of claim 1-7, its feature
It is, including：By diisocyanate, PEPA, end hydroxy butadiene, nano silicon, organosilicon, nano-silica
Change titanium, modified additive, modified graphene oxide, sulfur, dicyandiamide, Firebrake ZB, Silane coupling reagent KH-570, antioxidant, solidification
Agent, cross-linking agent and foaming agent are sufficiently stirred for, mix, and are subsequently adding polyethylene terephthalate, are stirring evenly and then adding into water
Mix, then pour compressing in 80-140 DEG C of insulation in mould, standing 20-40min into immediately, be put into 120-140 in baking oven
DEG C ripening 5-8h, adds the demoulding after releasing agent to obtain plate body, is then covered with copper sheet, copper sheet surface-pressure, room temperature on plate body surface
4-6h is stood, room temperature is cooled to and is obtained high rigidity heat-resistant anticorrosive polyurethane sheet.
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| CN107266901A (en) * | 2017-08-07 | 2017-10-20 | 青阳县吉祥塑胶有限公司 | A kind of high hardness polyurethane synthetic plastic filler and preparation method thereof |
| CN107841895A (en) * | 2017-10-19 | 2018-03-27 | 无为县荣华鬃刷制品有限公司 | A kind of heat-resisting Anti-fade dyestuff for the printing and dyeing of pig hair |
| CN108219437A (en) * | 2017-12-28 | 2018-06-29 | 安徽天择化工有限公司 | A kind of polyurethane of high rigidity and preparation method thereof |
| CN108948720A (en) * | 2018-06-25 | 2018-12-07 | 董小琳 | A kind of preparation method of TPU ventilated membrane |
| CN112501916A (en) * | 2020-11-23 | 2021-03-16 | 罗华先 | High-temperature-resistant corrosion-resistant glass fiber electronic cloth and preparation method thereof |
| CN112501916B (en) * | 2020-11-23 | 2023-01-06 | 山东兴国大成电子材料有限公司 | High-temperature-resistant corrosion-resistant glass fiber electronic cloth and preparation method thereof |
| CN115821574A (en) * | 2020-11-23 | 2023-03-21 | 罗华先 | High-temperature-resistant corrosion-resistant glass fiber electronic cloth |
| CN112457657A (en) * | 2020-11-30 | 2021-03-09 | 山东一诺威聚氨酯股份有限公司 | Thermoplastic polyurethane elastomer material for dustproof, antibacterial and self-cleaning film and preparation method thereof |
| CN114000263A (en) * | 2021-11-22 | 2022-02-01 | 上海楚桦仪器科技有限公司 | Full-automatic production method of anti-floc-falling non-woven fabric and clinical full-protection medical surgical drape |
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Application publication date: 20170426 |