CN104311768B - Polyurethane foam material, catalyst thereof and preparation method of catalyst - Google Patents
Polyurethane foam material, catalyst thereof and preparation method of catalyst Download PDFInfo
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- CN104311768B CN104311768B CN201410662645.1A CN201410662645A CN104311768B CN 104311768 B CN104311768 B CN 104311768B CN 201410662645 A CN201410662645 A CN 201410662645A CN 104311768 B CN104311768 B CN 104311768B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
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- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/08—Processes
- C08G18/16—Catalysts
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6622—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
The invention discloses a polyurethane foam material, a catalyst of the polyurethane foam material and a preparation method of the catalyst. The preparation method of the rare earth catalyst includes the following steps that (1), an absolute ethyl alcohol solution of ethylenediamine and an absolute ethyl alcohol solution of salicylaldehyde are mixed and react to obtain Schiff base; (2), the Schiff base obtained in the step (1) is dissolved in absolute ethyl alcohol to form a Schiff base solution, the Schiff base solution and an absolute ethyl alcohol solution of cerium chloride are mixed and react to obtain the rare earth catalyst. The rare earth catalyst is added to replace a traditional organic metal catalyst and a traditional rare earth isocaprylate catalyst, cost is reduced, catalysis singleness does not exist any more, the catalyst has lower toxicity and brings less harmfulness to human bodies and the environment, and the foaming time is controlled well, so that the prepared polyurethane foam material is low in heat conduction and higher in dimensional stability and has a certain functional effect and special antiviral and antibacterial functions, the stripping time is short, and foam cells are more even.
Description
Technical field
The present invention relates to a kind of polyurethane foamed material and catalyst thereof, and preparation method.
Background technology
Polyurethane foamed material is with its superior physics and chemistry combination property in recent years, it has also become auto parts and components are such as
The main material of the auto parts machinery product manufacturing such as medicated cushion, steering wheel, guard shield, handrail.Polyurethane foam material
Material is by polyhydric alcohol and diisocyanate or polyisocyanates shape under the effect of catalyst and other auxiliary agent
Become.Along with polyurethane foamed material research being goed deep into and the requirement of environmental conservation, high-performance and environmental protection
The polyurethane foamed material manufacturing technology of type becomes the emphasis of recent domestic research.It is used for by research and development
The novel raw material of synthesis of polyurethane foamed materials, such as foaming agent, isocyanates, catalyst etc., other help
Agent, makes the performance of polyurethane foamed material be greatly improved, greatly reduces production process and product simultaneously
The product pollution to environment.
People started amine, modified amine catalyst are launched research in recent years, and high to some environment-friendly types
The metal-organic catalyst prod report of acting type is few, and use during current domestic production is basic
Or traditional organotin and aminated compounds.The tradition such as stannous octoate, dibutyl tin laurate is organic
The catalyst of stannum class polyurethane foam, its unstable chemcial property, the most oxidized, poisonous and to environment
Cause harm.At present in polyurethane foamed material preparation process, traditional organic heavy metal catalysis of use
System can not meet the requirement of development of modern industry at the aspect such as product quality and environmental protection.
In recent years, the catalyst preparing polyurethane foamed material be have also been made in a large number by domestic and international scientific worker
Research work, mainly has slaine, the big class of trimethylamine two.Many organic/rare earth metals and organic metal
Compound has catalysis activity to the reaction between isocyanates and hydroxyl, and these metal major parts were in
Cross metal area, possess the general character of transition metal, there is higher metal activity, metal chelating can be formed
Compound and coordination compound.The catalyst of polyurethane foamed material is can be used for after preparation.
Existing rare earth catalyst is mainly isooctoate of rare earth metal class catalyst, and isooctyl acid class rare earth catalyst becomes
This is higher, and needs isooctoate of rare earth metal and isooctyl acid organometallic catalysts compound use to can be only achieved and urge
Change effect.In prior art, isooctyl acid class rare earth catalyst catalysis characteristics is single, only at " rare earth catalyst
Applied research in MDI type polyurethane track material " etc. several relevant reports have general introduction, urging
Change the aspects such as other foamed products of polyurethane (hard, soft, from skinning) and rarely have report.
Existing conventional organometallic catalysts is Organic leadP/hydrargyrum (Pb/Hg) composite catalyst and has
Machine lead/zinc (Pb/Zn) composite catalyst, lead/hydrargyrum is toxic heavy metal, on the one hand pollutes environment, one
Aspect can be absorbed by the body again, and infringement people's is healthy, adds conventional organometallic catalysts
It is the most excellent to there is performance in the polyurethane foam products that catalysis prepares, and foamed time is difficult to control to, during the demoulding
Between the problem such as long.
Summary of the invention
The technical problem to be solved is to overcome tradition organic tin catalyst in prior art
Unstable chemcial property, the most oxidized and poisonous to bad environmental, i.e. use tradition organic heavy metal to urge
Change system can not meet the requirement of development of modern industry to aspects such as polyurethane foam material quality and environmental protection,
Foamed time is difficult to control to, and the demoulding time is long, and isooctyl acid class rare earth catalyst cost in prior art
Higher, be only capable of with isooctyl acid organometallic catalysts compound use can be only achieved catalytic effect, catalysis spy
Property single defect, it is provided that a kind of polyurethane foamed material and catalyst thereof, and preparation method.This
The bright addition by rare earth catalyst instead of traditional organometallic catalysts and isooctoate of rare earth metal class
Catalyst, reduces cost, is catalyzed no longer unicity, has the character of more low toxicity, to human body and environment
Having had less hazardness, foamed time has obtained good control, makes the polyurethane foam material prepared
Material has that low thermal conductance, demoulding time is short, foam cell evenly advantage more preferable with dimensional stability.
The present invention solves above-mentioned technical problem by the following technical programs.
The invention provides the preparation method of a kind of rare earth catalyst, it comprises the following steps:
(1) being mixed with the ethanol solution of salicylide by the ethanol solution of ethylenediamine, reaction is i.e.
Obtain Schiff's base；
(2) Schiff's base of step (1) gained is dissolved in dehydrated alcohol and forms Schiff's base solution, by Schiff
Aqueous slkali mixes with the ethanol solution of cerous chlorate, and reaction i.e. obtains rare earth catalyst.
In step (1), described ethylenediamine is preferably 1:2～1:2.3 with the mol ratio of described salicylide.
In step (1), in the ethanol solution of described ethylenediamine, the volume fraction of ethylenediamine is preferable
Ground is 25%～40%.In the ethanol solution of described salicylide, the volume fraction of salicylide is preferably
It is 15%～30%.
In step (1), the temperature of described reaction is preferably 80～90 DEG C.The time of described reaction
Preferably 0.5h～3h.
In step (1), described reaction the most also carries out last handling process after terminating, described after
Processing procedure be preferably comprised standing to room temperature, sucking filtration, wash, be dried, recrystallization and after drying.
The preferred solvents ground of described washing is dehydrated alcohol.The preferred solvents ground of described recrystallization is dehydrated alcohol.
In step (2), described Schiff's base is preferably 2:1～3:1 with the mol ratio of described cerous chlorate.
In step (2), the concentration of described Schiff's base solution is preferably 0.5～0.8mol/L.
In step (2), the concentration of the ethanol solution of described cerous chlorate is preferably
0.25～0.4mol/L.
In step (2), the temperature of described reaction is preferably 80～90 DEG C.The time of described reaction
Preferably 1～4h.
In step (2), described Schiff's base solution is preferably Schiff's base and 55～75 DEG C of dehydrated alcohol
Mixing, the solution that constant temperature stirring 0.5～1h obtains.
In step (2), the ethanol solution of described cerous chlorate preferably by cerous chlorate with
55～75 DEG C of dehydrated alcohol mixing, the solution that constant temperature stirring 0.5～1h obtains.
In step (2), the operating process of described mixing is preferably by the nothing of described cerous chlorate
Hydrous ethanol solution is added drop-wise in described Schiff's base solution.
In step (2), after the end of described reaction, the most also carry out last handling process, described
Last handling process be preferably comprised standing to room temperature, sucking filtration, wash and be dried.The solvent of described washing
Preferably dehydrated alcohol.
In the present invention, room temperature generally refers to 10～30 DEG C.
Present invention also offers a kind of rare earth catalyst prepared by above-mentioned preparation method.
Present invention also offers a kind of polyhydric alcohol conjugate A material, it includes the component of following portions by weight: many
Unit's alcohol 100 parts, above-mentioned rare earth catalyst 0.1～0.3 part, triethylene diamine 0.1～2 parts, silicone oil 0.5～2
Part, ethylene glycol 0.5～10 parts, triethanolamine 1～3 parts and water 1～6 parts；Described polyhydric alcohol is polyethers
Polyhydric alcohol and/or PEPA.
Present invention also offers a kind of polyhydric alcohol conjugate A material, it is made up of the component of following portions by weight:
Polyhydric alcohol 100 parts, above-mentioned rare earth catalyst 0.1～0.3 part, triethylene diamine 0.1～2 parts, silicone oil 0.5～2
Part, ethylene glycol 0.5～10 parts, triethanolamine 1～3 parts and water 1～6 parts；Described polyhydric alcohol is polyethers
Polyhydric alcohol and/or PEPA.
Preferably a kind of polyhydric alcohol conjugate A of the present invention expects, it is made up of the component of following portions by weight: many
Unit's alcohol 100 parts, above-mentioned rare earth catalyst 0.1 part, triethylene diamine 2 parts, silicone oil 0.5 part, second two
Alcohol 1 part, triethanolamine 1 part and 1 part of water；Described polyhydric alcohol is polyether polyol and/or polyester polyols
Alcohol.
Wherein, described polyether polyol is preferably polyether polyol MJ-4110, polyether polyol
One or more in MA-330N and polyether polyol POP3628；Wherein, described polyether polyols
Alcohol MJ-4110 and described polyether polyol POP3628 are that Lianyun Harbour Mai Jia Chemical Co., Ltd. produces,
Described polyether polyol MA-330N is the commercial goods of the Central Asia, Changzhou Chemical Co., Ltd..
Wherein, described PEPA is preferably polyester FC-402 and/or polyester 3150-6；Wherein,
The described commercially available prod that polyester FC-402 is Jiangsu Qianglin Biologicgal Energy Co., Ltd, described polyester
3150-6 is that really high-tech adhesive company limited of Shandong China produces.Described PEPA preferably with institute
The polyether polyol stated is compounding to be used.When described PEPA compounds with described polyether polyol,
Preferably, the addition of described PEPA is 5～30% to described compounding ratio, wherein,
The PEPA that described percentage ratio is described accounts for the mass percent of described polyhydric alcohol total amount.
Wherein, the silico-carbo structure silicone oil of the polysiloxane-polyether copolymer that described silicone oil is the most conventional,
Preferably silicone oil SD-201 and/or dimethicone H201-100, wherein silicone oil SD-201 is Suzhou
Si De new material Science and Technology Ltd. commercially available prod, dimethicone H201-100 is traditional Chinese medicines group chemistry
The commercially available prod of reagent company limited.
Present invention also offers a kind of polyurethane raw material composition, it includes described polyhydric alcohol conjugate A material
And isocyanates.
Wherein, described isocyanates can be isocyanates commonly used in the art, the most sub-
Methyl many phenyl isocyanate PM200, modified diphenylmethane diisocyanate 103C and modified hexichol
One or more in dicyclohexylmethane diisocyanate 2460M.
Wherein, described polyhydric alcohol conjugate A material is preferably with the mass ratio of described isocyanates
1.03:1～1.36:1.
Present invention also offers the preparation method of a kind of polyurethane foamed material, it comprises the following steps: will
Described polyurethane raw material composition hybrid reaction, foaming forms polyurethane foamed material.
Wherein, before described polyurethane raw material composition hybrid reaction, polyhydric alcohol conjugate A material is preferably first
Carry out mechanical agitation.The time of described stirring is preferably 15～30min.
Wherein, described polyurethane raw material composition hybrid reaction is preferably placed in mould foaming, described
The temperature of mould be preferably 40～60 DEG C.
Wherein, the time of described foaming is preferably 7s～300s.
On the basis of meeting common sense in the field, above-mentioned each optimum condition, can combination in any, i.e. get Ben Fa
Bright each preferred embodiments.
Agents useful for same of the present invention and raw material are the most commercially.
The most progressive effect of the present invention is:
1, triethylene diamine coordinates rare earth catalyst to have higher catalysis activity, and consumption is less, can contract
The short reaction time, promote reaction selectively；
2, the rare earth catalyst of the present invention instead of isooctoate of rare earth metal catalyst and traditional organic metal is urged
Agent, reduces cost, improves the catalysis unicity of catalyst, shortens the demoulding time, during foaming
Between obtained good control, make to decrease environmental pollution and the harm to people.
3, rare earth catalyst can be good at controlling gel reaction and the relative velocity of foamable reaction, controls
The speed being suitable for is conducive to reacting best, and the abscess of foam is evenly more preferable with dimensional stability, foam
Heat conductivity reduce, improve the quality of finished product.And the polyurethane foam product tool that the present invention prepares
There is certain functional effect, there is antiviral, antibacterial specific function.
4, the manual foaming of the formula that the present invention uses and mechanical foaming all may be used, it is possible to resolve do not reach in condition
In the case of mechanical foaming, manual foam production polyurethane foam, general conditions ratio is relatively low, it is not necessary to big
The mechanical foaming equipment of scale also can complete foaming process.
Accompanying drawing explanation
Fig. 1 is hard polyurethane foams microscope figure, and wherein, A is the product of embodiment 1 preparation, B
Product for comparative example 1 preparation.
Fig. 2 is semi-hard polyurethane foam microscope figure, and wherein, A is the product of embodiment 2 preparation,
B is the product of comparative example 2 preparation.
Fig. 3 is semi-rigid polyurethane integral skin foam microscope figure, and wherein, A is embodiment 4 preparation
Product, B is the product of comparative example 4 preparation.
Fig. 4 is flexible polyurethane foams microscope figure, and wherein, A is the product of embodiment 6 preparation, B
Product for comparative example 6 preparation.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore limit the present invention to
Among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to often
Rule method and condition, or select according to catalogue.
Embodiment 1
(1) rare earth catalyst is prepared:
1. in the there-necked flask of 250ml, add 0.350mol salicylide and 100ml ethanol solution,
It is uniformly mixed；Separatory drop bottle is slowly added to 0.170mol ethylenediamine solution and 30ml dehydrated alcohol
Mixed liquor, be heated to 80 DEG C, condensing reflux 1h, obtain yellow mixed liquor.Stand and have yellow to room temperature
Crystal separates out, sucking filtration, absolute ethanol washing 3 times, and sucking filtration obtains sample, and air dry oven is dried 3h,
Dehydrated alcohol recrystallization, vacuum drying oven is dried 2h, obtains flat crystal Schiff's base.
2. 60 DEG C of dehydrated alcohol of 0.0138mol Schiff's base and 20ml that step is 1. prepared are mixed, permanent
Temperature 60 DEG C stirring 0.5h；60 DEG C of dehydrated alcohol of 0.00659mol cerous chlorate and 20ml mix, constant temperature 60 DEG C
The solution of cerous chlorate, to 80 DEG C of backflows, is slowly added dropwise in Schiff aqueous slkali by stirring 0.5h post-heating,
Reaction 3h, obtains grey-brown powder precipitation.Stand a few hours to room temperature.Sucking filtration 20min, dehydrated alcohol is washed
Washing 3 times, electric drying oven with forced convection is dried 3h, and vacuum drying oven is dried 2h, obtains rare earth catalyst.
(2) a kind of rigid polyurethane foam, it includes the component of following portions by weight:
Polyhydric alcohol conjugate A expects: polyether polyol MJ-4110 100 parts, rare earth catalyst 0.1 part, three
Ethylene diamine 2 parts, dimethicone H201-100 0.5 part, ethylene glycol 1 part, triethanolamine 1 part,
1 part of water.
Isocyanates PM200 100 parts.
1. polyhydric alcohol conjugate A is expected mechanical agitation 20min mix homogeneously；
2. the polyhydric alcohol conjugate A material mixing 1. isocyanates PM200 mixed homogeneously with step, machinery
Stirring 10s, obtain compound, compound is poured into rapidly mould temperature and is 50 DEG C and scribbles the mould of releasing agent,
Foaming 60s, forms polyurethane foam.
Comparative example 1
Rare earth catalyst is changed into the stannous octoate of equivalent, foams according to above-mentioned formula and foaming method,
Compare with demoulding time, heat conductivity and the foam size stability of polyurethane foam obtained above.
Embodiment 2
(1) rare earth catalyst is prepared:
1. in the there-necked flask of 250ml, add 0.33mol salicylide and 100ml ethanol solution, stir
Mix mix homogeneously；Separatory drop bottle is slowly added to 0.165mol ethylenediamine and the mixing of 30ml dehydrated alcohol
Liquid, is heated to 80 DEG C, and condensing reflux 1h obtains yellow mixed liquor.Standing has yellow crystals to analyse to room temperature
Going out, sucking filtration, absolute ethanol washing 3 times, sucking filtration obtains sample, and air dry oven is dried 3h, anhydrous second
Alcohol recrystallization, vacuum drying oven is dried 2h, obtains flat crystal Schiff's base.
2. 60 DEG C of dehydrated alcohol of 0.0138mol Schiff's base and 20ml that step is 1. prepared are mixed, permanent
Temperature 60 DEG C stirring 0.5h；60 DEG C of dehydrated alcohol of 0.00659mol cerous chlorate and 20ml mix, constant temperature 60 DEG C
The solution of cerous chlorate, to 80 DEG C of backflows, is slowly added dropwise in Schiff aqueous slkali by stirring 0.5h post-heating,
Reaction 3h, obtains grey-brown powder precipitation.Stand a few hours to room temperature.Sucking filtration 20min, dehydrated alcohol is washed
Washing 3 times, electric drying oven with forced convection is dried 3h, and vacuum drying oven is dried 2h, obtains rare earth catalyst.
(2) a kind of semi-hard polyurethane foamed materials, it includes the component of following portions by weight:
Polyhydric alcohol conjugate A expects: polyether polyol MA-330N 100 parts, rare earth catalyst 0.1 part,
Triethylene diamine 0.5 part, silicone oil SD-201 1 part, ethylene glycol 10 parts, triethanolamine 1 part, water 5
Part.
Isocyanates 103C 100 parts.
1. polyhydric alcohol conjugate A is expected mechanical agitation 20min mix homogeneously；
2. the polyhydric alcohol conjugate A 1. mixed homogeneously with step by isocyanates 103C expects mechanical agitation 10s,
Mix to obtain compound, compound is poured into rapidly mould temperature and is 50 DEG C and scribbles the mould of releasing agent, foaming
90s forms polyurethane foam.
Comparative example 2
Rare earth catalyst is changed into the stannous octoate of equivalent, foams according to above-mentioned formula and foaming method,
Compare with demoulding time, heat conductivity and the foam size stability of polyurethane foam obtained above.
Embodiment 3
(1) rare earth catalyst is prepared:
1. in the there-necked flask of 250ml, add 0.33mol salicylide and 95ml ethanol solution, stir
Mix mix homogeneously；Separatory drop bottle is slowly added to 0.165mol ethylenediamine solution and 25ml without dehydrated alcohol
Mixed liquor, be heated to 80 DEG C, condensing reflux 1h, obtain yellow mixed liquor.Stand and have yellow to room temperature
Crystal separates out, sucking filtration, absolute ethanol washing 3 times, and sucking filtration obtains sample, and air dry oven is dried 3h,
Dehydrated alcohol recrystallization, vacuum drying oven is dried 2h, obtains flat crystal Schiff's base.
2. 60 DEG C of dehydrated alcohol of 0.0138mol Schiff's base and 20ml that step is 1. prepared are mixed, permanent
Temperature 60 DEG C stirring 0.5h；60 DEG C of dehydrated alcohol of 0.00659mol cerous chlorate and 20ml mix, constant temperature 60 DEG C
The solution of cerous chlorate, to 80 DEG C of backflows, is slowly added dropwise in Schiff aqueous slkali by stirring 0.5h post-heating,
Reaction 3h, obtains grey-brown powder precipitation.Stand a few hours to room temperature.Sucking filtration 20min, dehydrated alcohol is washed
Washing 3 times, electric drying oven with forced convection is dried 3h, and vacuum drying oven is dried 2h, obtains rare earth catalyst.
(2) a kind of semi-hard polyurethane foamed materials, it includes the component of following portions by weight:
Polyhydric alcohol conjugate A expects: polyether polyol MJ-4110 100 parts, rare earth catalyst 0.1 part, three second
Alkene diamidogen 0.1 part, silicone oil SD-201 1 part, ethylene glycol 10 parts, triethanolamine 1 part, 5 parts of water.
Isocyanates 103C 95 parts.
1. polyhydric alcohol conjugate A material machinery is stirred 30min mix homogeneously；
2. by isocyanates 103C and step 1. in the polyhydric alcohol conjugate A that stirs expect mechanical agitation
10s, mixes to obtain compound, compound is poured into rapidly mould temperature and is 50 DEG C and scribbles the mould of releasing agent,
Foaming 100s forms polyurethane foam.
Comparative example 3
Rare earth catalyst is changed into the stannous octoate of equivalent, foams according to above-mentioned formula and foaming method,
Compare with demoulding time, heat conductivity and the foam size stability of polyurethane foam obtained above.
Embodiment 4
(1) rare earth catalyst is prepared:
1. in the there-necked flask of 250ml, add 0.33mol salicylide and 100ml ethanol solution, stir
Mix mix homogeneously；Separatory drop bottle is slowly added to 0.165mol ethylenediamine solution and 30ml dehydrated alcohol
Mixed liquor, is heated to 80 DEG C, and condensing reflux 1h obtains yellow mixed liquor.Standing room temperature has yellow brilliant
Body separates out, and sucking filtration, absolute ethanol washing 3 times, sucking filtration obtains sample, and air dry oven is dried 3h, nothing
Water-ethanol recrystallization, vacuum drying oven is dried 2h, obtains flat crystal Schiff's base.
2. 60 DEG C of dehydrated alcohol of 0.0138mol Schiff's base and 20ml that step is 1. prepared are mixed, permanent
Temperature 60 DEG C stirring 0.5h；60 DEG C of dehydrated alcohol of 0.00659mol cerous chlorate and 20ml mix, constant temperature 60 DEG C
The solution of cerous chlorate, to 80 DEG C of backflows, is slowly added dropwise in Schiff aqueous slkali by stirring 0.5h post-heating,
Reaction 3h, obtains grey-brown powder precipitation.Stand a few hours to room temperature.Sucking filtration 20min, dehydrated alcohol is washed
Washing 3 times, electric drying oven with forced convection is dried 3h, and vacuum drying oven is dried 2h, obtains rare earth catalyst.
(2) a kind of semi-rigid polyurethane integral skin foam material, it includes the component of following portions by weight:
Polyhydric alcohol conjugate A expects: polyether polyol 3,682 100 parts, rare earth catalyst 0.1 part, three second
Alkene diamidogen 1 part, silicone oil SD-201 1 part, ethylene glycol 10 parts, triethanolamine 1 part, 6 parts of water.
Isocyanates 103C 98 parts.
1. polyhydric alcohol conjugate A is expected mechanical agitation 30min mix homogeneously；
2. the polyhydric alcohol conjugate A that 1. isocyanates 103C mixs homogeneously with step expects mechanical agitation 10s,
Mix to obtain compound, compound is poured into rapidly mould temperature and is 50 DEG C and scribbles the mould of releasing agent, foaming
100s forms polyurethane foam.
Comparative example 4
Rare earth catalyst is changed into the stannous octoate of equivalent, foams according to above-mentioned formula and foaming method,
Compare with demoulding time, heat conductivity and the foam size stability of polyurethane foam obtained above.
Embodiment 5
(1) rare earth catalyst is prepared:
1. in the there-necked flask of 250ml, add 0.66mol salicylide and 200ml ethanol solution, stir
Mix mix homogeneously；Separatory drop bottle is slowly added to 0.32mol ethylenediamine solution and 60ml dehydrated alcohol
Mixed liquor, is heated to 80 DEG C, and condensing reflux 1h obtains yellow mixed liquor.Standing room temperature has yellow brilliant
Body separates out, and sucking filtration, absolute ethanol washing 3 times, sucking filtration obtains sample, and air dry oven is dried 3h, nothing
Water-ethanol recrystallization, vacuum drying oven is dried 2h, obtains flat crystal Schiff's base.
2. 60 DEG C of dehydrated alcohol of 0.0138mol Schiff's base and 20ml that step is 1. prepared are mixed, permanent
Temperature 60 DEG C stirring 0.5h；60 DEG C of dehydrated alcohol of 0.00659mol cerous chlorate and 20ml mix, constant temperature 60 DEG C
The solution of cerous chlorate, to 80 DEG C of backflows, is slowly added dropwise in Schiff aqueous slkali by stirring 0.5h post-heating,
Reaction 3h, obtains grey-brown powder precipitation.Stand a few hours to room temperature.Sucking filtration 20min, dehydrated alcohol is washed
Washing 3 times, electric drying oven with forced convection is dried 3h, and vacuum drying oven is dried 2h, obtains rare earth catalyst.
(2) a kind of rigid polyurethane foam, it includes the component of following portions by weight:
Polyhydric alcohol conjugate A expects: polyether polyol MJ-4110 95 parts, PEPA FC-402 5
Part, rare earth catalyst 0.1 part, triethylene diamine 2 parts, silicone oil SD-201 0.5 part, ethylene glycol 1 part,
Triethanolamine 1 part, 1 part of water.
Isocyanates PM200 100 parts.
1. polyhydric alcohol conjugate A is expected mechanical agitation 20min mix homogeneously；
2. the polyhydric alcohol conjugate A material mixing 1. isocyanates PM200 mixed homogeneously with step, machinery
Stirring 10s, obtain compound, compound is poured into rapidly mould temperature and is 50 DEG C and scribbles the mould of releasing agent,
Foaming 60s, forms polyurethane foam.
Comparative example 5
Rare earth catalyst is changed into the stannous octoate of equivalent, foams according to above-mentioned formula and foaming method,
Compare with demoulding time, heat conductivity and the foam size stability of polyurethane foam obtained above.
Embodiment 6
(1) rare earth catalyst is prepared:
1. in the there-necked flask of 250ml, add 0.37mol salicylide and 100ml ethanol solution, stir
Mix mix homogeneously；Separatory drop bottle is slowly added to 0.165mol ethylenediamine solution and 30ml dehydrated alcohol
Mixed liquor, is heated to 80 DEG C, and condensing reflux 1h obtains yellow mixed liquor.Standing room temperature has yellow brilliant
Body separates out, and sucking filtration, absolute ethanol washing 3 times, sucking filtration obtains sample, and air dry oven is dried 3h, nothing
Water-ethanol recrystallization, vacuum drying oven is dried 2h, obtains flat crystal Schiff's base.
2. 60 DEG C of dehydrated alcohol of 0.015mol Schiff's base and 20ml that step is 1. prepared are mixed, constant temperature
60 DEG C of stirring 0.5h；60 DEG C of dehydrated alcohol of 0.0075mol cerous chlorate and 20ml mix, constant temperature 60 DEG C
The solution of cerous chlorate, to 80 DEG C of backflows, is slowly added dropwise in Schiff aqueous slkali by stirring 0.5h post-heating,
Reaction 3h, obtains grey-brown powder precipitation.Stand a few hours to room temperature.Sucking filtration 20min, dehydrated alcohol is washed
Washing 3 times, electric drying oven with forced convection is dried 3h, and vacuum drying oven is dried 2h, obtains rare earth catalyst.
(2) a kind of flexible polyurethane foams, it includes the component of following portions by weight:
Polyhydric alcohol conjugate A expects: polyether polyol POP3628 100 parts, rare earth catalyst 0.1 part, three
Ethylene diamine 1 part, silicone oil SD-201 1 part, ethylene glycol 10 parts, triethanolamine 1 part, 6 parts of water.
Isocyanates 2460M 95 parts.
1. polyhydric alcohol conjugate A expects mechanical agitation 20min mix homogeneously；
2. the polyhydric alcohol conjugate A material mixing 1. isocyanates 2460M mixed homogeneously with step, machinery
Stirring 10s, obtain compound, compound is poured into rapidly mould temperature and is 50 DEG C and scribbles the mould of releasing agent,
Foaming 60s, forms polyurethane foam.
Comparative example 6
Rare earth catalyst is changed into the stannous octoate of equivalent, foams according to above-mentioned formula and foaming method,
Compare with demoulding time, heat conductivity and the foam size stability of polyurethane foam obtained above.
Embodiment 7
(1) rare earth catalyst is prepared:
1. in the there-necked flask of 250ml, add 0.33mol salicylide and 100ml ethanol solution, stir
Mix mix homogeneously；Separatory drop bottle is slowly added to 0.165mol ethylenediamine solution and 30ml dehydrated alcohol
Mixed liquor, is heated to 80 DEG C, and condensing reflux 1h obtains yellow mixed liquor.Standing room temperature has yellow brilliant
Body separates out, and sucking filtration, absolute ethanol washing 3 times, sucking filtration obtains sample, and air dry oven is dried 3h, nothing
Water-ethanol recrystallization, vacuum drying oven is dried 2h, obtains flat crystal Schiff's base.
2. 60 DEG C of dehydrated alcohol of 0.0138mol Schiff's base and 20ml that step is 1. prepared are mixed, permanent
Temperature 60 DEG C stirring 0.5h；60 DEG C of dehydrated alcohol of 0.00659mol cerous chlorate and 20ml mix, constant temperature 60 DEG C
The solution of cerous chlorate, to 80 DEG C of backflows, is slowly added dropwise in Schiff aqueous slkali by stirring 0.5h post-heating,
Reaction 3h, obtains grey-brown powder precipitation.Stand a few hours to room temperature.Sucking filtration 20min, dehydrated alcohol is washed
Washing 3 times, electric drying oven with forced convection is dried 3h, and vacuum drying oven is dried 2h, obtains rare earth catalyst.
(2) a kind of rigid polyurethane foam, it includes the component of following portions by weight:
Polyhydric alcohol conjugate A expects: polyether polyol MJ-4110 85 parts, PEPA FC-402 15
Part, rare earth catalyst 0.3 part, triethylene diamine 2 parts, silicone oil SD-201 0.5 part, ethylene glycol 1 part,
Triethanolamine 1 part, 1 part of water.
Isocyanates PM200 98 parts.
1. polyhydric alcohol conjugate A is expected mechanical agitation 15min mix homogeneously；2. by isocyanates PM200
1. the polyhydric alcohol conjugate A material mixing mixed homogeneously with step, mechanical agitation 10s, obtain compound, will be mixed
Closing material to pour rapidly mould temperature into and be 40 DEG C and scribble the mould of releasing agent, foam 60s, form polyurethane foam
Foam.
Comparative example 7
Rare earth catalyst is changed into the stannous octoate of equivalent, foams according to above-mentioned formula and foaming method,
Compare with demoulding time, heat conductivity and the foam size stability of polyurethane foam obtained above.
Embodiment 8
(1) rare earth catalyst is prepared:
1. in the there-necked flask of 250ml, add 0.33mol salicylide and 100ml ethanol solution, stir
Mix mix homogeneously；Separatory drop bottle is slowly added to 0.165mol ethylenediamine solution and 30ml dehydrated alcohol
Mixed liquor, is heated to 80 DEG C, and condensing reflux 1h obtains yellow mixed liquor.Standing room temperature has yellow brilliant
Body separates out, and sucking filtration, absolute ethanol washing 3 times, sucking filtration obtains sample, and air dry oven is dried 3h, nothing
Water-ethanol recrystallization, vacuum drying oven is dried 2h, obtains flat crystal Schiff's base.
2. 60 DEG C of dehydrated alcohol of 0.0138mol Schiff's base and 20ml that step is 1. prepared are mixed, permanent
Temperature 60 DEG C stirring 0.5h；60 DEG C of dehydrated alcohol of 0.00659mol cerous chlorate and 20ml mix, constant temperature 60 DEG C
The solution of cerous chlorate, to 80 DEG C of backflows, is slowly added dropwise in Schiff aqueous slkali by stirring 0.5h post-heating,
Reaction 3h, obtains grey-brown powder precipitation.Stand a few hours to room temperature.Sucking filtration 20min, dehydrated alcohol is washed
Washing 3 times, electric drying oven with forced convection is dried 3h, and vacuum drying oven is dried 2h, obtains rare earth catalyst.
(2) a kind of rigid polyurethane foam, it includes the component of following portions by weight:
Polyhydric alcohol conjugate A expects: polyether polyol MJ-4110 70 parts, PEPA FC-402 30
Part, rare earth catalyst 0.1 part, triethylene diamine 2 parts, silicone oil SD-201 0.5 part, ethylene glycol 0.5
Part, triethanolamine 1 part, 1 part of water.
Isocyanates PM200 98 parts.
1. polyhydric alcohol conjugate A is expected mechanical agitation 20min mix homogeneously；
2. the polyhydric alcohol conjugate A material mixing 1. isocyanates PM200 mixed homogeneously with step, machinery
Stirring 10s, obtain compound, compound is poured into rapidly mould temperature and is 60 DEG C and scribbles the mould of releasing agent,
Foaming 60s, forms polyurethane foam.
Comparative example 8
Rare earth catalyst is changed into the stannous octoate of equivalent, foams according to above-mentioned formula and foaming method,
Compare with demoulding time, heat conductivity and the foam size stability of polyurethane foam obtained above.
Embodiment 9
(1) rare earth catalyst is prepared:
1. in the there-necked flask of 250ml, add 0.35mol salicylide and 100ml ethanol solution, stir
Mix mix homogeneously；Separatory drop bottle is slowly added to 0.175mol ethylenediamine solution and 30ml dehydrated alcohol
Mixed liquor, is heated to 80 DEG C, and condensing reflux 1h obtains yellow mixed liquor.Standing room temperature has yellow brilliant
Body separates out, and sucking filtration, absolute ethanol washing 3 times, sucking filtration obtains sample, and air dry oven is dried 3h, nothing
Water-ethanol recrystallization, vacuum drying oven is dried 2h, obtains flat crystal Schiff's base.
2. 60 DEG C of dehydrated alcohol of 0.014mol Schiff's base and 20ml that step is 1. prepared are mixed, constant temperature
60 DEG C of stirring 0.5h；60 DEG C of dehydrated alcohol of 0.007mol cerous chlorate and 20ml mix, and constant temperature 60 DEG C stirs
Mix 0.5h post-heating to 80 DEG C of backflows, the solution of cerous chlorate be slowly added dropwise in Schiff aqueous slkali,
Reaction 3h, obtains grey-brown powder precipitation.Stand a few hours to room temperature.Sucking filtration 20min, dehydrated alcohol is washed
Washing 3 times, electric drying oven with forced convection is dried 3h, and vacuum drying oven is dried 2h, obtains rare earth catalyst.
(2) a kind of rigid polyurethane foam, it includes the component of following portions by weight:
Polyhydric alcohol conjugate A expects: polyether polyol MJ-4110 90 parts, PEPA 3150-6 10 parts,
Rare earth catalyst 0.1 part, triethylene diamine 2 parts, dimethicone H201-100 0.5 part, ethylene glycol
1 part, triethanolamine 1 part, 1 part of water.
Isocyanates PM200 100 parts.
1. polyhydric alcohol conjugate A expects mechanical agitation 20min mix homogeneously；
2. the polyhydric alcohol conjugate A material mixing 1. isocyanates PM200 mixed homogeneously with step, machinery
Stirring 10s, obtain compound, compound is poured into rapidly mould temperature and is 50 DEG C and scribbles the mould of releasing agent,
Foaming 60s, forms polyurethane foam.
Comparative example 9
The synthetic method of isooctyl acid cerium:
In there-necked flask, add a certain amount of isooctyl acid and sodium hydroxide solution, enter under heating quickly stirring
Row saponification 30min.Adding 200# solvent naphtha, dropwise dropping cerous chlorate solution, reacts one section
Time.Question response terminates, and product is poured into separatory funnel, stratification.Separate water layer and oil reservoir, oil
Being product mutually, aqueous phase is transferred in volumetric flask standby.Wherein, 200# solvent naphtha is the trade of Guangzhou power state
Company limited sells.
Rare earth catalyst is changed into the isooctyl acid cerium of equivalent, foams according to above-mentioned formula and foaming method,
Compare with demoulding time, heat conductivity and the foam size stability of polyurethane foam obtained above.
Effect example 1
Rare earth composite catalyst according to above-described embodiment 1-9 gained is catalyzed full water polyurethane foam,
The rare earth catalyst full water polyurethane of catalysis is replaced to send out by the foam obtained with stannous octoate or isooctyl acid cerium
The foam that obtains of bubble is made comparisons, and record demoulding time, the most at room temperature ripening are measured after 72 hours and led
Hot coefficient and foam size stability thereof.Indices is as shown in table 1 below.
The demoulding time of table 1 polyurethane foam, heat conductivity and foam size stability
| Sample | Demoulding time/S | Heat conductivity λ/w m-1·k-1 | Size changing rate/% (maintains 0 DEG C, 30d) |
| Embodiment 1 | 248 | 0.0292 | 0.051 |
| Comparative example 1 | 275 | 0.0354 | 0.162 |
| Embodiment 2 | 306 | 0.0309 | 0.065 |
| Comparative example 2 | 325 | 0.0398 | 0.119 |
| Embodiment 3 | 211 | 0.0203 | 0.061 |
| Comparative example 3 | 236 | 0.0304 | 0.132 |
| Embodiment 4 | 257 | 0.0214 | 0.094 |
| Comparative example 4 | 271 | 0.0316 | 0.185 |
| Embodiment 5 | 223 | 0.0238 | 0.016 |
| Comparative example 5 | 280 | 0.0285 | 0.048 |
| Embodiment 6 | 260 | 0.0218 | 0.013 |
| Comparative example 6 | 275 | 0.0263 | 0.089 |
| Embodiment 7 | 250 | 0.0288 | 0.049 |
| Comparative example 7 | 273 | 0.0351 | 0.148 |
| Embodiment 8 | 231 | 0.0232 | 0.023 |
| Comparative example 8 | 282 | 0.0281 | 0.057 |
| Embodiment 9 | 244 | 0.0281 | 0.032 |
| Comparative example 9 | 265 | 0.0325 | 0.089 |
As shown in Table 1, the polyurethane foam comparison ratio using technical scheme to prepare is implemented
Foam prepared by example 1-9, the shortening of demoulding time, significantly improve production rate；There is lower heat
Lead coefficient, improve heat-insulating property；There is lower size changing rate, improve the steady of polyurethane foam
Qualitative.
Effect example 2
Fig. 1 is hard polyurethane foams microscope figure, and wherein, A is the hard polyurethane of embodiment 1 preparation
Ester froth pulp, B is the polyurethane foam products of comparative example 1 preparation.As shown in Figure 1, implement
The hard polyurethane foams pore structure of example 1 preparation is more attractive, and foam size is evenly.
Fig. 2 is semi-hard polyurethane foam microscope figure, and wherein, A is the semi-rigid of embodiment 2 preparation
Polyurethane foam products, B is the polyurethane foam products of comparative example 2 preparation.As shown in Figure 2,
Embodiment 2 preparation semi-hard polyurethane foam pore structure more attractive, foam size evenly, Fault Segment
Less compared with the product of stannous octoate catalyst system and catalyzing.
Fig. 3 is semi-rigid polyurethane integral skin foam microscope figure, and wherein, A is embodiment 4 preparation
Semi-rigid polyurethane integral skin foam product, B is the polyurethane foam products of comparative example 4 preparation.
From the figure 3, it may be seen that the semi-rigid polyurethane integral skin foam pore structure of embodiment 4 preparation is more attractive, foam
Size is evenly.
Fig. 4 is the flexible polyurethane foams microscope figure of preparation, and wherein, A is the soft of embodiment 6 preparation
Matter polyurethane foam products, B is the polyurethane foam products of comparative example 6 preparation.As shown in Figure 4,
The flexible polyurethane foams pore structure of embodiment 6 preparation is more attractive, and evenly, Fault Segment is relatively for foam size
The product of stannous octoate catalyst system and catalyzing is less.
Claims (9)
1. polyhydric alcohol conjugate A material, it is characterised in that it includes the component of following portions by weight:
Polyhydric alcohol 100 parts, rare earth catalyst 0.1～0.3 part, triethylene diamine 0.1～2 parts, silicone oil 0.5～2 parts,
Ethylene glycol 0.5～10 parts, triethanolamine 1～3 parts and water 1～6 parts；Described polyhydric alcohol is polyether polyols
Alcohol and/or PEPA；
Wherein, the preparation method of described rare earth catalyst comprises the following steps:
(1) being mixed with the ethanol solution of salicylide by the ethanol solution of ethylenediamine, reaction is i.e.
Obtain Schiff's base；
(2) Schiff's base of step (1) gained is dissolved in dehydrated alcohol and forms Schiff's base solution, by Schiff
Aqueous slkali mixes with the ethanol solution of cerous chlorate, and reaction i.e. obtains rare earth catalyst.
2. polyhydric alcohol conjugate A material as claimed in claim 1, it is characterised in that in step (1),
Described ethylenediamine is 1:2～1:2.3 with the mol ratio of described salicylide；
In step (1), in the ethanol solution of described ethylenediamine, the volume fraction of ethylenediamine is
25%～40%；In the ethanol solution of described salicylide, the volume fraction of salicylide is 15%～30%；
In step (1), the temperature of described reaction is 80～90 DEG C；The time of described reaction is 0.5～3h；
In step (1), described reaction also carries out last handling process, described post processing after terminating
Journey include standing to room temperature, sucking filtration, wash, be dried, recrystallization and after drying；Described washing molten
Agent is dehydrated alcohol；The solvent of described recrystallization is dehydrated alcohol.
3. polyhydric alcohol conjugate A material as claimed in claim 1, it is characterised in that in step (2),
Described Schiff's base is 2:1～3:1 with the mol ratio of described cerous chlorate；
In step (2), the concentration of described Schiff's base solution is 0.5～0.8mol/L；
In step (2), the concentration of the ethanol solution of described cerous chlorate is 0.25～0.4mol/L；
In step (2), the temperature of described reaction is 80～90 DEG C；The time of described reaction is 1～4h；
In step (2), described Schiff's base solution is by Schiff's base and 55～75 DEG C of dehydrated alcohol mixing,
The solution that constant temperature stirring 0.5～1h obtains；
In step (2), the ethanol solution of described cerous chlorate is by cerous chlorate and 55～75 DEG C
Dehydrated alcohol mixes, the solution that constant temperature stirring 0.5～1h obtains；
In step (2), the operating process of described mixing is by the dehydrated alcohol of described cerous chlorate
Solution is added drop-wise in described Schiff's base solution；
In step (2), after the end of described reaction, also carry out last handling process, described post processing
Process includes standing to room temperature, sucking filtration, washs and be dried；The solvent of described washing is dehydrated alcohol.
4. polyhydric alcohol conjugate A material as claimed in claim 1, it is characterised in that it is by following weight
The component composition of number: polyhydric alcohol 100 parts, rare earth catalyst 0.1～0.3 part, triethylene diamine 0.1～2
Part, silicone oil 0.5～2 parts, ethylene glycol 0.5～10 parts, triethanolamine 1～3 parts and water 1～6 parts；Described
Polyhydric alcohol is polyether polyol and/or PEPA.
5. the polyhydric alcohol conjugate A material as described in any one of Claims 1 to 4, it is characterised in that described
Polyether polyol be polyether polyol MJ-4110, polyether polyol MA-330N and polyether polyol
One or more in POP3628；Described PEPA is polyester FC-402 and/or polyester
3150-6；Described silicone oil is silicone oil SD-201 and/or dimethicone H201-100；
And/or, described PEPA is compounding with described polyether polyol to be used；When described polyester
When polyhydric alcohol and described polyether polyol compound, described compounding ratio is, described polyester polyols
The addition of alcohol is 5～30%, and wherein, the PEPA that described percentage ratio is described accounts for described polynary
The mass percent of alcohol total amount.
6. a polyurethane raw material composition, it is characterised in that it includes as claim 1-5 is arbitrary
Polyhydric alcohol conjugate A material described in Xiang and isocyanates.
7. polyurethane raw material composition as claimed in claim 6, it is characterised in that described isocyanide
Acid esters is polymethylene multi-phenenyl isocyanate PM200, modified diphenylmethane diisocyanate 103C
With one or more in modified diphenylmethane diisocyanate 2460M；Described polyhydric alcohol conjugate A
Material is 1.03:1～1.36:1 with the mass ratio of described isocyanates.
8. the preparation method of a polyurethane foamed material, it is characterised in that it comprises the following steps:
By polyurethane raw material composition hybrid reaction as claimed in claims 6 or 7, foaming forms polyurethane foam
Foam material.
9. preparation method as claimed in claim 8, it is characterised in that described urethane raw group
Before compound hybrid reaction, polyhydric alcohol conjugate A material first carries out mechanical agitation；The time of described stirring is
15～30min；
Described polyurethane raw material composition hybrid reaction is placed in mould foaming, the temperature of described mould
It it is 40～60 DEG C；
The time of described foaming is 7s～300s.
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| US6811815B2 (en) * | 2002-06-14 | 2004-11-02 | Avery Dennison Corporation | Method for roll-to-roll deposition of optically transparent and high conductivity metallic thin films |
| CN101812083A (en) * | 2009-07-16 | 2010-08-25 | 黑龙江大学 | Salicylaldehyde diamine rear earth coordination compound and synthesis method and application thereof |
| CN103087114B (en) * | 2013-01-30 | 2016-06-22 | 苏州大学 | A kind of Salalen type rare-earth metal amide and its preparation method and application |
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