CN106626169B - A kind of polyurethane aqueous release agent - Google Patents
A kind of polyurethane aqueous release agent Download PDFInfo
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- CN106626169B CN106626169B CN201611044003.0A CN201611044003A CN106626169B CN 106626169 B CN106626169 B CN 106626169B CN 201611044003 A CN201611044003 A CN 201611044003A CN 106626169 B CN106626169 B CN 106626169B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
- B29C33/64—Silicone
Abstract
The present invention provides a kind of polyurethane aqueous release agents, by weight, including：1~60 part of paraffin；1~50 part of modified siloxane polymer；2~10 parts of emulsifier；10~15 parts of surfactant；100~150 parts of deionized water；Wherein modified siloxane polymer average molecular weight ranging from 2000~6000.Polyurethane aqueous release agent provided by the invention, which has, repeated multiple times to be used, and stripping result is excellent, the feature of the polyurethane product quality height and releasing agent holding time length that are prepared.Economic cost, time cost and human cost are largely saved.
Description
Technical field
The present invention relates to polyurethane material ejection technique field, more particularly it relates to which a kind of polyurethane is with aqueous
Releasing agent.
Background technology
Releasing agent is a kind of functional materials between mold and finished product, can prevent the elastomers such as rubber, plastics and
The product of other materials is bonded on die surface, plays the role of a kind of processing aid of assisted demoulding.In order to weaken plastics system
Absorption or bonding between product and mold, using the releasing agent that can form effective isolation film, the object for being easy to adhesion for two
Surface forms a dielectric film layer, these releasing agents form micron order thickness, heat-staple film layer, chemistry is formed with die surface
Connection makes to be formed between adhesive and material to be bonded and be isolated so that peeling force decrease, can allow profiled part quickly easily
It falls off.
Polyurethane aqueous release agent is when using external release agent, it is necessary to which solvent is processed into solution, emulsion or dispersion
It after body, can just be uniformly distributed on mold wall, therefore the selection of solvent also seems very important.Common organic solvents are often
It is comparatively ideal improved method with toxicity or combustibility, therefore with water substitution organic solvent, and safe and environment-friendly.Develop water
Property releasing agent also will be as the development trend of new liquid releasing agent from now on.Polyurethane still has one with aqueous release agent at present
A little problems, such as：Access times are limited, cannot repeatedly be used for a long time, and are finished and just need to clear up, increase time and manpower at
This, stripping result is poor.Therefore there is an urgent need for one kind to be used for a long time, and is not limited by access times, and stripping result is good, demoulding
Efficient new polyurethane aqueous release agent.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of polyurethane aqueous release agents.
In order to achieve the above-mentioned object of the invention, this invention takes following technical schemes：
A kind of polyurethane aqueous release agent, by weight, including：
Wherein modified siloxane polymer average molecular weight ranging from 2000~6000.
As a kind of perferred technical scheme, the polyurethane aqueous release agent, by weight, including：
Wherein modified siloxane polymer average molecular weight ranging from 2000~6000.
As a kind of perferred technical scheme, in the polyurethane aqueous release agent contained modified siloxane polymer with
The mass ratio of paraffin is 1：(2~4).
As a kind of perferred technical scheme, in the polyurethane aqueous release agent contained modified siloxane polymer with
The mass ratio of paraffin is 1：(2.5~3.5).
As a kind of perferred technical scheme, the modified siloxane polymer is the poly- methyl that ferrocene derivatives are modified
Hydrogen siloxane.
As a kind of perferred technical scheme, the structure that the polymethyl hydrogen siloxane that the ferrocene derivatives are modified contains
Unit is：
As a kind of perferred technical scheme, the mass ratio of the ferrocene derivatives and the polymethyl hydrogen siloxane is
1：(3~5.75).
As a kind of perferred technical scheme, the emulsifier is selected from the one or two of sorbester p17 or Tween 80.
As a kind of perferred technical scheme, the surfactant is sodium alkyl benzene sulfonate.
Another aspect of the present invention provides a kind of preparation method of polyurethane aqueous release agent, includes the following steps：
Paraffin is added in flask, modified siloxane polymer, emulsifier, surfactant is under the conditions of 100~150 DEG C
It is uniformly mixed, polyurethane aqueous release agent presoma is prepared；
Deionized water is added in conical flask, and deionized water is heated to 70~85 DEG C；
The deionized water of heat in step (2) is added in the releasing agent presoma in step (1), at a temperature of 80~85 DEG C
Stir 3~5h after, at room temperature stir 30~45min to get.
Compared with prior art, beneficial effects of the present invention：
Polyurethane provided by the invention is with aqueous release agent due to the poly- methyl hydrogen silica that is modified with ferrocene derivatives
There is interaction and the hole transporting property of the metal-Metal of space transmission, electronics to enliven depth height for alkane, wherein ferrocene,
Since the presence with amido bond in molecule forms hydrophobic pocket with solvent water molecules, such pocket is existing for metal electron
Under the conditions of, can ion be continuously drawn from hydrone and form multilayer self-assembled film, when releasing agent being made to work in a mold, be easy to make
Polyurethane is removed with mold, and is used multiple times.Releasing agent is free-moving due to having in ferrocene derivatives at work
Electronics so that form weak interface layer in polyurethane and releasing agent surface, in polyurethane when removing demoulding, releasing agent is not turned
It moves, there is high demoulding efficiency.
Specific implementation mode
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
Those skilled in the art of the present technique are appreciated that unless otherwise defined, all terms used herein (including technology art
Language and scientific terminology) there is meaning identical with the general understanding of the those of ordinary skill in fields of the present invention.Should also
Understand, those terms such as defined in the general dictionary, which should be understood that, to be had and the meaning in the context of the prior art
The consistent meaning of justice, and unless defined as here, will not be with idealizing or the meaning of too formal be explained.
A kind of polyurethane aqueous release agent, by weight, including：
Wherein modified siloxane polymer average molecular weight ranging from 2000~6000.
Polyurethane releasing agent
Polyurethane material is a kind of high molecular material for being widely used in industry, national defence etc., due to its raw material and is matched
Than multifarious feature, so as to cause the diversity of polymer architecture performance.Polyurethane aqueous release agent of the present invention
Required releasing agent when being molded mainly for polyurethane foam plastics.
In polyurethane moulded processing, the product to obtain any surface finish uses releasing agent.Ideal releasing agent
Should have preferable thermal stability and chemical stability, not corrode mold, in the not remaining decomposition product of die surface；It should be able to give and make
The good appearance of product, does not influence color and luster, adhesiveness of product etc.；It should require the mold cleaning time as few as possible；Answer nontoxic, peace
Entirely, easy to operation.
Paraffin：
Paraffin is one kind of refinery products, is one kind of mineral wax and one kind of pertroleum wax.It is steamed from crude oil
Slack wax is made through solvent refining, solvent dewaxing or through wax freezing and crystallizing, squeezing dewaxing in the lube cut for evaporating gained, then through solvent
De-oiling, it is refined obtained by sheet or acicular crystal.
Paraffin used in the present invention is selected from Guangzhou Chen Xin Chemical Co., Ltd.s, trade mark 300#, purity >=99%.
Modified siloxane polymer
The present invention (buys from the limited public affairs of this reagent of Adama commercially available polymethyl hydrogen siloxane using ferrocene derivatives
Department, specification 100g) it is modified.Specific preparation method is as follows：
1. the synthesis of ferrocene derivatives.
At room temperature, 1,1'- diacetyl ferrocenes (are bought from lark prestige Science and Technology Ltd., specification 5g, purity
97%) it is dissolved in sodium hypochlorite (NaOCl) solution, is warming up to 50 DEG C or so 1 hour of reaction, be continuously heating to 80 DEG C of heating 1
After a hour, NaOCl solution is added, the reaction was continued 18 hours.It filters while hot, filtrate is neutralized to pH=1 with concentrated hydrochloric acid, has
A large amount of yellow mercury oxide generates.It filters, precipitation is dissolved with NaOH solution, then is acidified with concentrated hydrochloric acid, and filtered solid is in room temperature
Under dry, obtain crocus solid to get the double formic acid of ferrocene.
The double acyl chlorides synthesis of ferrocene：The double formic acid of above-mentioned ferrocene are weighed, are added into there-necked flask, stirring is lower to add CH2C12, pyrrole
Pyridine is stirred under ice bath, and CH is measured2C12, it is added in vacuum dropper, and oxalyl chloride is added, in N after mixing2It is added dropwise under gas shielded,
Time for adding is not less than 1 hour；It is stirred 4 hours under ice bath, then removes ice bath, reaction at room temperature is stayed overnight；Reflux is changed to,
After being heated to reflux 4 hours, CH is steamed under decompression2C12, repeatedly extracted on a small quantity with petroleum ether, merge extracting solution, stone is steamed under decompression
Oily ether, obtains dark red solid.It is spare to be flushed with hydrogen gas shielded.
It takes ferrocene formyl chloride to be dissolved in dichloromethane, then adds to N, N- dimethyl-ethylenediamines, triethylamine, dichloro dropwise
In the mixed solution of methane.It is stirred to react 16h at room temperature, stops reaction.Reaction solution NaHCO3Aqueous solution washing 3 times, then
With anhydrous MgSO4Washing, is removed under reduced pressure solvent, obtains filemot solid product.Yellowish-brown and triethylamine are dissolved in solution
In, acryloyl chloride is then added dropwise, after ice bath reacts 2 hours, then reacts at room temperature 12 hours.After reaction, filtering is anti-
Solution is answered to remove unreacted reactant.After collecting filtrate, it is evaporated under reduced pressure to obtain product.Crude product is purified by silica gel chromatographic column,
Pure solid is finally dried to obtain orange solids in 40 DEG C of vacuum drying ovens.
The structural formula of synthesized ferrocene derivatives is as follows：
2. the synthetic method of modified siloxane polymer.
(1) ferrocene derivatives and polymethyl hydrogen siloxane are placed in flask, carry out removing water pre- place under vacuum
Reason.
(2) it is added pretreated raw material in step (1) in flask, toluene, phenolic inhibitor, under the conditions of nitrogen protection,
It is uniformly mixed, increases temperature to 50~55 DEG C, after stirring 5~7min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h
~5h.
(3) reaction solution in step (2) is cooled to room temperature.To obtain the final product.
The mass ratio of the ferrocene derivatives and the polymethyl hydrogen siloxane is preferably 1：(3~5.75), further
Preferably 1：(4~5).
Emulsifier
Emulsifier belongs to surfactant, is that emulsion can be helped to form and keep stable substance.Due to can be with shape
At micella, so playing important function in emulsion polymerization.But and not all surfactant all can serve as emulsifier,
Effective stabilization only played to polymer emulsion system, at the same will not substance influential on polymerisation, be just suitble to
Make emulsifier.In emulsion process, oil is immiscible with water, is only to be not likely to form stable dispersion with stirring.
After emulsifier is added in the process for preparation of releasing agent, under the action of stirring, oil phase can form many drops, it
Surface can adsorb one layer of emulsifier.And the lipophilic group in emulsifier molecules stretches to drop internal, hydrophilic radical then with water phase
In conjunction with.Since there are electrostatic repulsion forces between drop, so being difficult to be combined into big drop by collision between droplet, then
The emulsion system stablized.So suitable emulsifier is selected to seem most important.
Emulsifier is selected from the one or two of sorbester p17 or Tween 80 in the present invention.
Surfactant
The present invention selects anion surfactant, preferably sodium alkyl benzene sulfonate.The foaming of polyurethane foam plastics
Journey is extremely complex, other than isocyanates and polyol reaction generate polyurethane chain reaction of propagation, in addition after demoulding, passes
In the aqueous release agent of system after the volatilization of most of water, thin moisture film is always left in a mold, in mold temperature 50~80
DEG C when, preferentially reacted with the isocyanate compound of polyurethane system and non-volatile, generate adamantine polyureas chemical combination
Object.This will largely effect on quality of forming film.Due to ring formation in polymer molecule in modified siloxane polymer, there is electron rich
Amido bond and anion surfactant act synergistically, prevent isocyanates to react generation polyurea compound with water.
The preparation method of polyurethane aqueous release agent includes the following steps in the present invention：
(1) it is added paraffin in flask, modified siloxane polymer, emulsifier, anion surfactant, 100~
It is uniformly mixed under the conditions of 150 DEG C, polyurethane aqueous release agent presoma is prepared；
(2) deionized water is added in conical flask, and deionized water is heated to 70~85 DEG C；
(3) deionized water of the heat in step (2) is added in the releasing agent presoma in step (1), 80~85 DEG C of temperature
After 3~5h of the lower stirring of degree, stir at room temperature 30~45min to get.
Polyurethane provided by the invention is with aqueous release agent due to the poly- methyl hydrogen silica that is modified with ferrocene derivatives
There is interaction and the hole transporting property of the metal-Metal of space transmission, electronics to enliven depth height for alkane, wherein ferrocene,
Since the presence with amido bond in molecule forms hydrophobic pocket with solvent water molecules, such pocket exists in metal electron
Under conditions of, can ion be continuously drawn from hydrone and form multilayer self-assembled film, when releasing agent being made to work in a mold, be easy to
So that polyurethane is removed with mold, and is used multiple times.Releasing agent is moved freely due to having in ferrocene derivatives at work
Electronics so that form weak interface layer on polyurethane and releasing agent surface, polyurethane remove demould when, releasing agent is not turned
It moves, there is high demoulding efficiency.
With reference to specific embodiment, the present invention is described in further detail.
It is commercially available that raw material of the present invention, which does not have specified otherwise,.
Embodiment 1
At room temperature, 1,1 '-diacetyl ferrocenes of 10g are dissolved in the 10%NaOCl solution of 260mL, are warming up to 50
It DEG C 1 hour of reaction, is continuously heating to 80 DEG C, after heating 1 hour, adds 120mL (10%) NaOCl solution, continue anti-
Answer 18 hours.It filters while hot, filtrate is neutralized to pH=1 with concentrated hydrochloric acid, has a large amount of yellow mercury oxide to generate.It filters, precipitation is used
NaOH solution dissolves, then is acidified with concentrated hydrochloric acid, and filtered solid natural air drying at room temperature obtains crocus solid.
The double acyl chlorides synthesis of ferrocene：Above-mentioned solid 5g is weighed, is added into 500mL there-necked flasks, is added with stirring 200mL
CH2Cl2, 1mL pyridines stir 25 minutes under ice bath：Measure 50mL CH2C12, it is added in vacuum dropper, and 20mL grass is added
Acyl chlorides, in N after mixing2Protection is lower to be added dropwise, and time for adding is not less than 1 hour；It is stirred 4 hours under ice bath, then removes ice bath, room
The lower reaction of temperature is overnight；It is changed to reflux, after being heated to reflux 4 hours, CH is steamed under decompression2C12, repeatedly carried on a small quantity with petroleum ether
It takes, merges extracting solution, steam petroleum ether under decompression, obtain dark red solid.
The above-mentioned dark red solids of 5g are dissolved in 20mL dichloromethane, then add to 5mL N, N- dimethyl second two dropwise
Amine, 5mL triethylamines, 15mL dichloromethane mixed solution in.It is stirred to react 16h at room temperature, stops reaction.Reaction solution 50mL
NaHCO3Aqueous solution (0.3w%) washs 3 times, then with anhydrous MgSO4Washing, is removed under reduced pressure solvent, obtains filemot solid
Product.Tan solid product and triethylamine (2mL) are dissolved in 150mL tetrahydrofuran solutions, propylene is then added dropwise
Acyl chlorides 1mL after ice bath reacts 2 hours, is then reacted at room temperature 12 hours.After reaction, filtering reacting solution removes unreacted
Object.After collecting filtrate, it is evaporated under reduced pressure to obtain product.Crude product is purified by silica gel chromatographic column, and finally pure solid exists
It is dried to obtain orange solids in 40 DEG C of vacuum drying ovens.
The above-mentioned ferrocene derivatives of 5g and polymethyl hydrogen siloxane 20g are placed in flask, are removed under vacuum
Water pretreatment.
It is added pretreated raw material in flask, toluene 100mL, methylnaphthohydroquinone 2g, under the conditions of nitrogen protection, stirring
It is uniformly mixed, increases temperature to 55 DEG C, after stirring 5min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h, is cooled to room temperature,
It is modified polymethyl hydrogen siloxane up to ferrocene derivatives.
The preparation method of polyurethane aqueous release agent, includes the following steps in the present invention：
(1) paraffin 30g, modified siloxane polymer 10g, Tween 80 (5g), sodium alkyl benzene sulfonate are added in flask
10g is uniformly mixed under the conditions of 150 DEG C, and polyurethane aqueous release agent presoma is prepared；(2) in conical flask
Deionized water 100g is added, and deionized water is heated to 85 DEG C；(3) step is added in the deionized water of the heat in step (2)
(1) in the releasing agent presoma in, at a temperature of 85 DEG C stir 5h after, at room temperature stir 45min to get.
Embodiment 2
At room temperature, 1,1 '-diacetyl ferrocenes of 10g are dissolved in the 10%NaOCl solution of 260mL, are warming up to 50
It DEG C 1 hour of reaction, is continuously heating to 80 DEG C, after heating 1 hour, adds 120mL (10%) NaOCl solution, continue anti-
Answer 18 hours.It filters while hot, filtrate is neutralized to pH=1 with concentrated hydrochloric acid, has a large amount of yellow mercury oxide to generate.It filters, precipitation is used
NaOH solution dissolves, then is acidified with concentrated hydrochloric acid, and filtered solid natural air drying at room temperature obtains crocus solid.
The double acyl chlorides synthesis of ferrocene：Above-mentioned solid 5g is weighed, is added into 500mL there-necked flasks, is added with stirring 200mL
CH2Cl2, 1mL pyridines stir 25 minutes under ice bath：Measure 50mL CH2C12, it is added in vacuum dropper, and 20mL grass is added
Acyl chlorides, in N after mixing2Protection is lower to be added dropwise, and time for adding is not less than 1 hour；It is stirred 4 hours under ice bath, then removes ice bath, room
The lower reaction of temperature is overnight；It is changed to reflux, after being heated to reflux 4 hours, CH is steamed under decompression2C12, repeatedly carried on a small quantity with petroleum ether
It takes, merges extracting solution, steam petroleum ether under decompression, obtain dark red solid.
The above-mentioned dark red solids of 5g are dissolved in 20mL dichloromethane, then add to 5mL N, N- dimethyl second two dropwise
Amine, 5mL triethylamines, 15mL dichloromethane mixed solution in.It is stirred to react 16h at room temperature, stops reaction.Reaction solution 50mL
NaHCO3Aqueous solution (0.3w%) washs 3 times, then with anhydrous MgSO4Washing, is removed under reduced pressure solvent, obtains filemot solid
Product.Tan solid product and triethylamine (2mL) are dissolved in 150mL tetrahydrofuran solutions, propylene is then added dropwise
Acyl chlorides 1mL after ice bath reacts 2 hours, is then reacted at room temperature 12 hours.After reaction, filtering reacting solution removes unreacted
Object.After collecting filtrate, it is evaporated under reduced pressure to obtain product.Crude product is purified by silica gel chromatographic column, and finally pure solid exists
It is dried to obtain orange solids in 40 DEG C of vacuum drying ovens.
The above-mentioned ferrocene derivatives of 5g and polymethyl hydrogen siloxane 15g are placed in flask, are removed under vacuum
Water pretreatment.
It is added pretreated raw material in flask, toluene 100mL, methylnaphthohydroquinone 2g, under the conditions of nitrogen protection, stirring is mixed
It closes uniformly, increases temperature to 55 DEG C, after stirring 5min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h, is cooled to room temperature, i.e.,
It obtains ferrocene derivatives and is modified polymethyl hydrogen siloxane.
The preparation method of polyurethane aqueous release agent, includes the following steps in the present invention：
(1) paraffin 20g, modified siloxane polymer 10g, sorbester p17 (8g), sodium alkyl benzene sulfonate are added in flask
10g is uniformly mixed under the conditions of 150 DEG C, and polyurethane aqueous release agent presoma is prepared；(2) in conical flask
Deionized water 100g is added, and deionized water is heated to 85 DEG C；(3) step is added in the deionized water of the heat in step (2)
(1) in the releasing agent presoma in, at a temperature of 85 DEG C stir 5h after, at room temperature stir 45min to get.
Embodiment 3
At room temperature, 1,1 '-diacetyl ferrocenes of 10g are dissolved in the 10%NaOCl solution of 260mL, are warming up to 50
It DEG C 1 hour of reaction, is continuously heating to 80 DEG C, after heating 1 hour, adds 120mL (10%) NaOCl solution, continue anti-
Answer 18 hours.It filters while hot, filtrate is neutralized to pH=1 with concentrated hydrochloric acid, has a large amount of yellow mercury oxide to generate.It filters, precipitation is used
NaOH solution dissolves, then is acidified with concentrated hydrochloric acid, and filtered solid natural air drying at room temperature obtains crocus solid.
The double acyl chlorides synthesis of ferrocene：Above-mentioned solid 5g is weighed, is added into 500mL there-necked flasks, is added with stirring 200mL
CH2Cl2, 1mL pyridines stir 25 minutes under ice bath：Measure 50mL CH2Cl2, it is added in vacuum dropper, and 20mL grass is added
Acyl chlorides, in N after mixing2Protection is lower to be added dropwise, and time for adding is not less than 1 hour；It is stirred 4 hours under ice bath, then removes ice bath, room
The lower reaction of temperature is overnight；It is changed to reflux, after being heated to reflux 4 hours, CH is steamed under decompression2Cl2, repeatedly carried on a small quantity with petroleum ether
It takes, merges extracting solution, steam petroleum ether under decompression, obtain dark red solid.
The above-mentioned dark red solids of 5g are dissolved in 20mL dichloromethane, then add to 5mL N, N- dimethyl second two dropwise
Amine, 5mL triethylamines, 15mL dichloromethane mixed solution in.It is stirred to react 16h at room temperature, stops reaction.Reaction solution 50mL
NaHCO3Aqueous solution (0.3w%) washs 3 times, then with anhydrous MgSO4Washing, is removed under reduced pressure solvent, obtains filemot solid
Product.Tan solid product and triethylamine (2mL) are dissolved in 150mL tetrahydrofuran solutions, propylene is then added dropwise
Acyl chlorides 1mL after ice bath reacts 2 hours, is then reacted at room temperature 12 hours.After reaction, filtering reacting solution removes unreacted
Object.After collecting filtrate, it is evaporated under reduced pressure to obtain product.Crude product is purified by silica gel chromatographic column, and finally pure solid exists
It is dried to obtain orange solids in 40 DEG C of vacuum drying ovens.
The above-mentioned ferrocene derivatives of 5g and polymethyl hydrogen siloxane 10g are placed in flask, are removed under vacuum
Water pretreatment.
It is added pretreated raw material in flask, toluene 100mL, methylnaphthohydroquinone 2g, under the conditions of nitrogen protection, stirring is mixed
It closes uniformly, increases temperature to 55 DEG C, after stirring 5min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h, is cooled to room temperature, i.e.,
It obtains ferrocene derivatives and is modified polymethyl hydrogen siloxane.
The preparation method of polyurethane aqueous release agent, includes the following steps in the present invention：
(1) paraffin 25g, modified siloxane polymer 10g, sorbester p17 (4g), sodium alkyl benzene sulfonate are added in flask
13g is uniformly mixed under the conditions of 150 DEG C, and polyurethane aqueous release agent presoma is prepared；(2) in conical flask
Deionized water 100g is added, and deionized water is heated to 85 DEG C；(3) step is added in the deionized water of the heat in step (2)
(1) in the releasing agent presoma in, at a temperature of 85 DEG C stir 5h after, at room temperature stir 45min to get.
Embodiment 4
At room temperature, 1,1 '-diacetyl ferrocenes of 10g are dissolved in the 10%NaOCl solution of 260mL, are warming up to 50
It DEG C 1 hour of reaction, is continuously heating to 80 DEG C, after heating 1 hour, adds 120mL (10%) NaOCl solution, continue anti-
Answer 18 hours.It filters while hot, filtrate is neutralized to pH=1 with concentrated hydrochloric acid, has a large amount of yellow mercury oxide to generate.It filters, precipitation is used
NaOH solution dissolves, then is acidified with concentrated hydrochloric acid, and filtered solid natural air drying at room temperature obtains crocus solid.
The double acyl chlorides synthesis of ferrocene：Above-mentioned solid 5g is weighed, is added into 500mL there-necked flasks, is added with stirring 200mL
CH2C12, 1mL pyridines stir 25 minutes under ice bath：Measure 50mL CH2C12, it is added in vacuum dropper, and 20mL grass is added
Acyl chlorides, in N after mixing2Protection is lower to be added dropwise, and time for adding is not less than 1 hour；It is stirred 4 hours under ice bath, then removes ice bath, room
The lower reaction of temperature is overnight；It is changed to reflux, after being heated to reflux 4 hours, CH is steamed under decompression2C12, repeatedly carried on a small quantity with petroleum ether
It takes, merges extracting solution, steam petroleum ether under decompression, obtain dark red solid.
The above-mentioned dark red solids of 5g are dissolved in 20mL dichloromethane, then add to 5mL N, N- dimethyl second two dropwise
Amine, 5mL triethylamines, 15mL dichloromethane mixed solution in.It is stirred to react 16h at room temperature, stops reaction.Reaction solution 50mL
NaHCO3Aqueous solution (0.3w%) washs 3 times, then with anhydrous MgSO4Washing, is removed under reduced pressure solvent, obtains filemot solid
Product.Tan solid product and triethylamine (2mL) are dissolved in 150mL tetrahydrofuran solutions, propylene is then added dropwise
Acyl chlorides 1mL after ice bath reacts 2 hours, is then reacted at room temperature 12 hours.After reaction, filtering reacting solution removes unreacted
Object.After collecting filtrate, it is evaporated under reduced pressure to obtain product.Crude product is purified by silica gel chromatographic column, and finally pure solid exists
It is dried to obtain orange solids in 40 DEG C of vacuum drying ovens.
The above-mentioned ferrocene derivatives of 5g and polymethyl hydrogen siloxane 28.75g are placed in flask, are carried out under vacuum
Except water pretreatment.
It is added pretreated raw material in flask, toluene 100mL, methylnaphthohydroquinone 2g, under the conditions of nitrogen protection, stirring is mixed
It closes uniformly, increases temperature to 55 DEG C, after stirring 5min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h, is cooled to room temperature, i.e.,
It obtains ferrocene derivatives and is modified polymethyl hydrogen siloxane.
The preparation method of polyurethane aqueous release agent, includes the following steps in the present invention：
(1) paraffin 10g, modified siloxane polymer 40g, sorbester p17 (5g), sodium alkyl benzene sulfonate are added in flask
12g is uniformly mixed under the conditions of 150 DEG C, and polyurethane aqueous release agent presoma is prepared；(2) in conical flask
Deionized water 100g is added, and deionized water is heated to 85 DEG C；(3) step is added in the deionized water of the heat in step (2)
(1) in the releasing agent presoma in, at a temperature of 85 DEG C stir 5h after, at room temperature stir 45min to get.
Embodiment 5
At room temperature, 1,1 '-diacetyl ferrocenes of 10g are dissolved in the 10%NaOCl solution of 260mL, are warming up to 50
It DEG C 1 hour of reaction, is continuously heating to 80 DEG C, after heating 1 hour, adds 120mL (10%) NaOCl solution, continue anti-
Answer 18 hours.It filters while hot, filtrate is neutralized to pH=1 with concentrated hydrochloric acid, has a large amount of yellow mercury oxide to generate.It filters, precipitation is used
NaOH solution dissolves, then is acidified with concentrated hydrochloric acid, and filtered solid natural air drying at room temperature obtains crocus solid.
The double acyl chlorides synthesis of ferrocene：Above-mentioned solid 5g is weighed, is added into 500mL there-necked flasks, is added with stirring 200mL
CH2C12, 1mL pyridines stir 25 minutes under ice bath：Measure 50mL CH2C12, it is added in vacuum dropper, and 20mL grass is added
Acyl chlorides, in N after mixing2Protection is lower to be added dropwise, and time for adding is not less than 1 hour；It is stirred 4 hours under ice bath, then removes ice bath, room
The lower reaction of temperature is overnight；It is changed to reflux, after being heated to reflux 4 hours, CH is steamed under decompression2C12, repeatedly carried on a small quantity with petroleum ether
It takes, merges extracting solution, steam petroleum ether under decompression, obtain dark red solid.
The above-mentioned dark red solids of 5g are dissolved in 20mL dichloromethane, then add to 5mL N, N- dimethyl second two dropwise
Amine, 5mL triethylamines, 15mL dichloromethane mixed solution in.It is stirred to react 16h at room temperature, stops reaction.Reaction solution 50mL
NaHCO3Aqueous solution (0.3w%) washs 3 times, then with anhydrous MgSO4Washing, is removed under reduced pressure solvent, obtains filemot solid
Product.Tan solid product and triethylamine (2mL) are dissolved in 150mL tetrahydrofuran solutions, propylene is then added dropwise
Acyl chlorides 1mL after ice bath reacts 2 hours, is then reacted at room temperature 12 hours.After reaction, filtering reacting solution removes unreacted
Object.After collecting filtrate, it is evaporated under reduced pressure to obtain product.Crude product is purified by silica gel chromatographic column, and finally pure solid exists
It is dried to obtain orange solids in 40 DEG C of vacuum drying ovens.
The above-mentioned ferrocene derivatives of 5g and polymethyl hydrogen siloxane 25g are placed in flask, are removed under vacuum
Water pretreatment.
It is added pretreated raw material in flask, toluene 100mL, methylnaphthohydroquinone 2g, under the conditions of nitrogen protection, stirring is mixed
It closes uniformly, increases temperature to 55 DEG C, after stirring 5min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h, is cooled to room temperature, i.e.,
It obtains ferrocene derivatives and is modified polymethyl hydrogen siloxane.
The preparation method of polyurethane aqueous release agent, includes the following steps in the present invention：
(1) paraffin 10g, modified siloxane polymer 20g, sorbester p17 (5g), sodium alkyl benzene sulfonate are added in flask
12g is uniformly mixed under the conditions of 150 DEG C, and polyurethane aqueous release agent presoma is prepared；(2) in conical flask
Deionized water 100g is added, and deionized water is heated to 85 DEG C；(3) step is added in the deionized water of the heat in step (2)
(1) in the releasing agent presoma in, at a temperature of 85 DEG C stir 5h after, at room temperature stir 45min to get.
Embodiment 6
At room temperature, 1,1 '-diacetyl ferrocenes of 10g are dissolved in the 10%NaOCl solution of 260mL, are warming up to 50
It DEG C 1 hour of reaction, is continuously heating to 80 DEG C, after heating 1 hour, adds 120mL (10%) NaOCl solution, continue anti-
Answer 18 hours.It filters while hot, filtrate is neutralized to pH=1 with concentrated hydrochloric acid, has a large amount of yellow mercury oxide to generate.It filters, precipitation is used
NaOH solution dissolves, then is acidified with concentrated hydrochloric acid, and filtered solid natural air drying at room temperature obtains crocus solid.
The double acyl chlorides synthesis of ferrocene：Above-mentioned solid 5g is weighed, is added into 500mL there-necked flasks, is added with stirring 200mL
CH2C12, 1mL pyridines stir 25 minutes under ice bath：Measure 50mL CH2C12, it is added in vacuum dropper, and 20mL grass is added
Acyl chlorides, in N after mixing2Protection is lower to be added dropwise, and time for adding is not less than 1 hour；It is stirred 4 hours under ice bath, then removes ice bath, room
The lower reaction of temperature is overnight；It is changed to reflux, after being heated to reflux 4 hours, CH is steamed under decompression2C12, repeatedly carried on a small quantity with petroleum ether
It takes, merges extracting solution, steam petroleum ether under decompression, obtain dark red solid.
The above-mentioned dark red solids of 5g are dissolved in 20mL dichloromethane, then add to 5mL N, N- dimethyl second two dropwise
Amine, 5mL triethylamines, 15mL dichloromethane mixed solution in.It is stirred to react 16h at room temperature, stops reaction.Reaction solution 50mL
NaHCO3Aqueous solution (0.3w%) washs 3 times, then with anhydrous MgSO4Washing, is removed under reduced pressure solvent, obtains filemot solid
Product.Tan solid product and triethylamine (2mL) are dissolved in 150mL tetrahydrofuran solutions, propylene is then added dropwise
Acyl chlorides 1mL after ice bath reacts 2 hours, is then reacted at room temperature 12 hours.After reaction, filtering reacting solution removes unreacted
Object.After collecting filtrate, it is evaporated under reduced pressure to obtain product.Crude product is purified by silica gel chromatographic column, and finally pure solid exists
It is dried to obtain orange solids in 40 DEG C of vacuum drying ovens.
The above-mentioned ferrocene derivatives of 5g and polymethyl hydrogen siloxane 23g are placed in flask, are removed under vacuum
Water pretreatment.
It is added pretreated raw material in flask, toluene 100mL, methylnaphthohydroquinone 2g, under the conditions of nitrogen protection, stirring is mixed
It closes uniformly, increases temperature to 55 DEG C, after stirring 5min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h, is cooled to room temperature, i.e.,
It obtains ferrocene derivatives and is modified polymethyl hydrogen siloxane.
The preparation method of polyurethane aqueous release agent, includes the following steps in the present invention：
(1) paraffin 10g, modified siloxane polymer 35g, Tween 80 (10g), sodium alkyl benzene sulfonate are added in flask
13g is uniformly mixed under the conditions of 140 DEG C, and polyurethane aqueous release agent presoma is prepared；(2) in conical flask
Deionized water 100g is added, and deionized water is heated to 80 DEG C；(3) deionized water of heat is added to the demoulding in step (1)
In agent presoma, at a temperature of 85 DEG C stir 5h after, at room temperature stir 45min to get.
Comparative example 1
The preparation method of polyurethane aqueous release agent, includes the following steps：
(1) paraffin 30g, modified siloxane polymer 10g, sorbester p17 (5g), sodium alkyl benzene sulfonate are added in flask
10g is uniformly mixed under the conditions of 150 DEG C, and polyurethane aqueous release agent presoma is prepared；(2) in conical flask
Deionized water 100g is added, and deionized water is heated to 85 DEG C；(3) step is added in the deionized water of the heat in step (2)
(1) in the releasing agent presoma in, at a temperature of 85 DEG C stir 5h after, at room temperature stir 45min to get.
Comparative example 2
At room temperature, 1,1 '-diacetyl ferrocenes of 10g are dissolved in the 10%NaOCl solution of 260mL, are warming up to 50
It DEG C 1 hour of reaction, is continuously heating to 80 DEG C, after heating 1 hour, adds 120mL (10%) NaOCl solution, continue anti-
Answer 18 hours.It filters while hot, filtrate is neutralized to pH=1 with concentrated hydrochloric acid, has a large amount of yellow mercury oxide to generate.It filters, precipitation is used
NaOH solution dissolves, then is acidified with concentrated hydrochloric acid, and filtered solid natural air drying at room temperature obtains crocus solid.
The double acyl chlorides synthesis of ferrocene：Above-mentioned solid 5g is weighed, is added into 500mL there-necked flasks, is added with stirring 200mL
CH2C12, 1mL pyridines stir 25 minutes under ice bath：Measure 50mL CH2C12, it is added in vacuum dropper, and 20mL grass is added
Acyl chlorides, in N after mixing2Protection is lower to be added dropwise, and time for adding is not less than 1 hour；It is stirred 4 hours under ice bath, then removes ice bath, room
The lower reaction of temperature is overnight；It is changed to reflux, after being heated to reflux 4 hours, CH is steamed under decompression2C12, repeatedly carried on a small quantity with petroleum ether
It takes, merges extracting solution, steam petroleum ether under decompression, obtain dark red solid.
The above-mentioned dark red solids of 5g are dissolved in 20mL dichloromethane, then add to 5mL N, N- dimethyl second two dropwise
Amine, 5mL triethylamines, 15mL dichloromethane mixed solution in.It is stirred to react 16h at room temperature, stops reaction.Reaction solution 50mL
NaHCO3Aqueous solution (0.3w%) washs 3 times, then with anhydrous MgSO4Washing, is removed under reduced pressure solvent, obtains filemot solid
Product.Tan solid product and triethylamine (2mL) are dissolved in 150mL tetrahydrofuran solutions, propylene is then added dropwise
Acyl chlorides 1mL after ice bath reacts 2 hours, is then reacted at room temperature 12 hours.After reaction, filtering reacting solution removes unreacted
Object.After collecting filtrate, it is evaporated under reduced pressure to obtain product.Crude product is purified by silica gel chromatographic column, and finally pure solid exists
It is dried to obtain orange solids in 40 DEG C of vacuum drying ovens.
The above-mentioned ferrocene derivatives of 5g and polymethyl hydrogen siloxane 10g are placed in flask, are removed under vacuum
Water pretreatment.
It is added pretreated raw material in flask, toluene 100mL, methylnaphthohydroquinone 2g, under the conditions of nitrogen protection, stirring is mixed
It closes uniformly, increases temperature to 55 DEG C, after stirring 5min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h, is cooled to room temperature, i.e.,
It obtains ferrocene derivatives and is modified polymethyl hydrogen siloxane.
The preparation method of polyurethane aqueous release agent, includes the following steps in the present invention：
(1) paraffin 50g, modified siloxane polymer 10g, Tween 80 (5g), sodium alkyl benzene sulfonate are added in flask
10g is uniformly mixed under the conditions of 150 DEG C, and polyurethane aqueous release agent presoma is prepared；(2) in conical flask
Deionized water 100g is added, and deionized water is heated to 85 DEG C；(3) step is added in the deionized water of the heat in step (2)
(1) in the releasing agent presoma in, at a temperature of 85 DEG C stir 5h after, at room temperature stir 45min to get.
Comparative example 3
At room temperature, 1,1 '-diacetyl ferrocenes of 10g are dissolved in the 10%NaOCl solution of 260mL, are warming up to 50
It DEG C 1 hour of reaction, is continuously heating to 80 DEG C, after heating 1 hour, adds 120mL (10%) NaOCl solution, continue anti-
Answer 18 hours.It filters while hot, filtrate is neutralized to pH=1 with concentrated hydrochloric acid, has a large amount of yellow mercury oxide to generate.It filters, precipitation is used
NaOH solution dissolves, then is acidified with concentrated hydrochloric acid, and filtered solid natural air drying at room temperature obtains crocus solid.
The double acyl chlorides synthesis of ferrocene：Above-mentioned solid 5g is weighed, is added into 500mL there-necked flasks, is added with stirring 200mL
CH2C12, 1mL pyridines stir 25 minutes under ice bath：Measure 50mL CH2C12, it is added in vacuum dropper, and 20mL grass is added
Acyl chlorides, in N after mixing2Protection is lower to be added dropwise, and time for adding is not less than 1 hour；It is stirred 4 hours under ice bath, then removes ice bath, room
The lower reaction of temperature is overnight；It is changed to reflux, after being heated to reflux 4 hours, CH is steamed under decompression2C12, repeatedly carried on a small quantity with petroleum ether
It takes, merges extracting solution, steam petroleum ether under decompression, obtain dark red solid.
The above-mentioned dark red solids of 5g are dissolved in 20mL dichloromethane, then add to 5mL N, N- dimethyl second two dropwise
Amine, 5mL triethylamines, 15mL dichloromethane mixed solution in.It is stirred to react 16h at room temperature, stops reaction.Reaction solution 50mL
NaHCO3Aqueous solution (0.3w%) washs 3 times, then with anhydrous MgSO4Washing, is removed under reduced pressure solvent, obtains filemot solid
Product.Tan solid product and triethylamine (2mL) are dissolved in 150mL tetrahydrofuran solutions, propylene is then added dropwise
Acyl chlorides 1mL after ice bath reacts 2 hours, is then reacted at room temperature 12 hours.After reaction, filtering reacting solution removes unreacted
Object.After collecting filtrate, it is evaporated under reduced pressure to obtain product.Crude product is purified by silica gel chromatographic column, and finally pure solid exists
It is dried to obtain orange solids in 40 DEG C of vacuum drying ovens.
The above-mentioned ferrocene derivatives of 5g and polymethyl hydrogen siloxane 60g are placed in flask, are removed under vacuum
Water pretreatment.
It is added pretreated raw material in flask, toluene 100mL, methylnaphthohydroquinone 2g, under the conditions of nitrogen protection, stirring is mixed
It closes uniformly, increases temperature to 55 DEG C, after stirring 5min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h, is cooled to room temperature, i.e.,
It obtains ferrocene derivatives and is modified polymethyl hydrogen siloxane.
The preparation method of polyurethane aqueous release agent, includes the following steps in the present invention：
(1) paraffin 10g, modified siloxane polymer 10g, Tween 80 (5g), sodium alkyl benzene sulfonate are added in flask
10g is uniformly mixed under the conditions of 150 DEG C, and polyurethane aqueous release agent presoma is prepared；(2) in conical flask
Deionized water 100g is added, and deionized water is heated to 85 DEG C；(3) step is added in the deionized water of the heat in step (2)
(1) in the releasing agent presoma in, at a temperature of 85 DEG C stir 5h after, at room temperature stir 45min to get.
Comparative example 4
At room temperature, 1,1 '-diacetyl ferrocenes of 10g are dissolved in the 10%NaOCl solution of 260mL, are warming up to 50
It DEG C 1 hour of reaction, is continuously heating to 80 DEG C, after heating 1 hour, adds 120mL (10%) NaOCl solution, continue anti-
Answer 18 hours.It filters while hot, filtrate is neutralized to pH=1 with concentrated hydrochloric acid, has a large amount of yellow mercury oxide to generate.It filters, precipitation is used
NaOH solution dissolves, then is acidified with concentrated hydrochloric acid, and filtered solid natural air drying at room temperature obtains crocus solid.
The double acyl chlorides synthesis of ferrocene：Above-mentioned solid 5g is weighed, is added into 500mL there-necked flasks, is added with stirring 200mL
CH2C12, 1mL pyridines stir 25 minutes under ice bath：Measure 50mL CH2C12, it is added in vacuum dropper, and 20mL grass is added
Acyl chlorides, in N after mixing2Protection is lower to be added dropwise, and time for adding is not less than 1 hour；It is stirred 4 hours under ice bath, then removes ice bath, room
The lower reaction of temperature is overnight；It is changed to reflux, after being heated to reflux 4 hours, CH is steamed under decompression2C12, repeatedly carried on a small quantity with petroleum ether
It takes, merges extracting solution, steam petroleum ether under decompression, obtain dark red solid.
The above-mentioned dark red solids of 5g are dissolved in 20mL dichloromethane, then add to 5mL N, N- dimethyl second two dropwise
Amine, 5mL triethylamines, 15mL dichloromethane mixed solution in.It is stirred to react 16h at room temperature, stops reaction.Reaction solution 50mL
NaHCO3Aqueous solution (0.3w%) washs 3 times, then with anhydrous MgSO4Washing, is removed under reduced pressure solvent, obtains filemot solid
Product.Tan solid product and triethylamine (2mL) are dissolved in 150mL tetrahydrofuran solutions, propylene is then added dropwise
Acyl chlorides 1mL after ice bath reacts 2 hours, is then reacted at room temperature 12 hours.After reaction, filtering reacting solution removes unreacted
Object.After collecting filtrate, it is evaporated under reduced pressure to obtain product.Crude product is purified by silica gel chromatographic column, and finally pure solid exists
It is dried to obtain orange solids in 40 DEG C of vacuum drying ovens.
The above-mentioned ferrocene derivatives of 5g and polymethyl hydrogen siloxane 20g are placed in flask, are removed under vacuum
Water pretreatment.
It is added pretreated raw material in flask, toluene 100mL, methylnaphthohydroquinone 2g, under the conditions of nitrogen protection, stirring is mixed
It closes uniformly, increases temperature to 55 DEG C, after stirring 5min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h, is cooled to room temperature, i.e.,
It obtains ferrocene derivatives and is modified polymethyl hydrogen siloxane.
The preparation method of polyurethane aqueous release agent, includes the following steps in the present invention：
(1) paraffin 30g, modified siloxane polymer 10g, Tween 80 (5g), cetyl trimethyl are added in flask
Ammonium bromide 10g is uniformly mixed under the conditions of 150 DEG C, and polyurethane aqueous release agent presoma is prepared；(2) it is boring
Deionized water 100g is added in shape bottle, and deionized water is heated to 85 DEG C；(3) deionized water of the heat in step (2) is added
Enter in the releasing agent presoma in step (1), at a temperature of 85 DEG C stir 5h after, at room temperature stir 45min to get.
Comparative example 5
Commercial polyurethane is foam-formed to use releasing agent.
Performance test
Releasing agent obtained by embodiment and comparative example is used as the molding of polyurethane foam product, and performance survey is carried out to it
Examination.Specific implementation mode：Die surface is cleaned with ethyl alcohol, mold is heated to 70 DEG C, in the uniform brushing releasing agent in its surface, and
Solvent is dried up with spray gun, then polyurethane foam virgin pulp liquid is uniformly poured into mold and is quickly stirred, thermal insulation foaming 10 minutes, die sinking
And take out polyurethane foam product.
Stripping result：Level-one：Upper and lower mould can be rapidly separated, die surface non-foam product residual, and product surface is flat
Whole, corner angle are clean and tidy, no breakage.
Two level：Upper mould surface has foamed product residual viscous, and lower mould surface non-foam product remains, and product surface is relatively flat
It is whole, no breakage.
Three-level：Upper mould surface non-foam product residual is viscous, and lower mould surface has foamed product residual, product surface relatively flat
It is whole, no breakage.
Level Four：Upper and lower mould can not be rapidly separated, and upper and lower mould has foamed product residual, and product surface out-of-flatness, corner angle have broken
Damage.
Pyatyi：Upper and lower mould can not be rapidly separated, and upper and lower mould has more foamed product to remain, the special out-of-flatness of product surface,
Corner angle are unclear, and product surface has breakage.
Surface contact angle：Releasing agent sample is laid on clean glass slide, waits for its film forming.Using German DSA100 types
Number droplet morphology analyzer.Test condition:Each sample chooses three different measurement points, measures static state of the water on its surface and connects
Feeler (3 μ L of droplet size), takes its average value.By software calculate to get.
1 the performance test results of table
It is obtained by the performance test of the embodiment and comparative example of table 1 as drawn a conclusion：
Polyurethane aqueous release agent provided by the invention, which is compared, to be had with releasing agent in comparative example and repeated multiple times can use,
Stripping result is excellent, the feature of the polyurethane product quality height and holding time length that are prepared.Largely save
About cost, saves manpower.
Polyurethane provided by the invention is with aqueous release agent due to the poly- methyl hydrogen silica that is modified with ferrocene derivatives
There is interaction and the hole transporting property of the metal-Metal of space transmission, electronics to enliven depth height for alkane, wherein ferrocene,
Since the presence with amido bond in molecule forms hydrophobic pocket with solvent water molecules, such pocket is existing for metal electron
Under the conditions of, can ion be continuously drawn from hydrone and form multilayer self-assembled film, when releasing agent being made to work in a mold, be easy to make
Polyurethane is removed with mold, and is used multiple times.Releasing agent is free-moving due to having in ferrocene derivatives at work
Electronics so that form weak interface layer in polyurethane and releasing agent surface, in polyurethane when removing demoulding, releasing agent is not turned
It moves, there is high demoulding efficiency.
Claims (5)
1. a kind of polyurethane aqueous release agent, which is characterized in that by weight, including：
The emulsifier is selected from the one or two of sorbester p17 or Tween 80；The quality of the modified siloxane polymer and paraffin
Than being 1：(2~4)；The modified siloxane polymer average molecular weight ranging from 2000~6000；The modified siloxane is poly-
It is the polymethyl hydrogen siloxane that ferrocene derivatives are modified to close object, and preparation method is：
(1) ferrocene derivatives and polymethyl hydrogen siloxane are placed in flask, carry out removing water pretreatment under vacuum；
(2) it is added pretreated raw material in step (1) in flask, toluene, phenolic inhibitor, under the conditions of nitrogen protection, stirring
It is uniformly mixed, increases temperature to 50~55 DEG C, after stirring 5~7min, chloroplatinic acid/Isopropanol catalysis agent is added, stirs 4h~5h；
(3) reaction solution in step (2) is cooled to room temperature to obtain the final product；
The mass ratio of the ferrocene derivatives and polymethyl hydrogen siloxane is 1：(3~5.75)；The ferrocene derivatives change
The structural unit that the polymethyl hydrogen siloxane of property contains is：
2. polyurethane aqueous release agent according to claim 1, which is characterized in that by weight, including：
Wherein modified siloxane polymer average molecular weight ranging from 2000~6000.
3. polyurethane aqueous release agent according to claim 1, which is characterized in that the polyurethane aqueous release agent
In the mass ratio of contained modified siloxane polymer and paraffin be 1：(2.5~3.5).
4. polyurethane aqueous release agent according to claim 1, which is characterized in that the anion surfactant is
Sodium alkyl benzene sulfonate.
5. the preparation method of polyurethane aqueous release agent according to any one of claims 1-4, which is characterized in that packet
Include following steps：
(1) paraffin is added in flask, modified siloxane polymer, emulsifier, surfactant is under the conditions of 100~150 DEG C
It is uniformly mixed, polyurethane aqueous release agent presoma is prepared；
(2) deionized water is added in conical flask, and deionized water is heated to 70~85 DEG C；
(3) deionized water of the heat in step (2) is added in the releasing agent presoma in step (1), at a temperature of 80~85 DEG C
Stir 3~5h after, at room temperature stir 30~45min to get.
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Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4020038C1 (en) * | 1990-06-23 | 1992-01-30 | Klueber-Chemie Kg, 8031 Maisach, De | Aq. release agent compsn. for polyurethane mouldings - contains parting agent, emulsifier, and at least partly saponified polyvinyl acetate |
| JP3290540B2 (en) * | 1994-05-23 | 2002-06-10 | 信越化学工業株式会社 | Release agent composition |
| US6162290A (en) * | 1998-05-28 | 2000-12-19 | Acmos Chemie Gmbh & Co. | Release agent |
| DE102007024493A1 (en) * | 2007-05-25 | 2008-11-27 | Evonik Goldschmidt Gmbh | Aqueous release agents and their use in the production of polyurethane moldings |
| DE102009005084A1 (en) * | 2009-01-16 | 2010-07-22 | Acmos Chemie Kg | Mold releasing agent, useful to prepare polyurethane molded body, comprises a carrier medium comprising water and/or organic solvents, a silicone polyglycolether and a release active substance comprising soap, oil, detergents or silicone |
| CN104260243A (en) * | 2014-07-30 | 2015-01-07 | 宁国市冠宇模具有限公司 | Polyurethane water-based release agent |
| CN105252678B (en) * | 2015-11-06 | 2017-11-14 | 沈阳化工大学 | A kind of high temperature resistant wax system environment-protecting polyurethane releasing agent and preparation method thereof |
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