CN107286306A - A kind of aqueous polyurethane acrylate copolymer emulsion and preparation method thereof - Google Patents
A kind of aqueous polyurethane acrylate copolymer emulsion and preparation method thereof Download PDFInfo
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- CN107286306A CN107286306A CN201710613842.8A CN201710613842A CN107286306A CN 107286306 A CN107286306 A CN 107286306A CN 201710613842 A CN201710613842 A CN 201710613842A CN 107286306 A CN107286306 A CN 107286306A
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
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- C08G18/40—High-molecular-weight compounds
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G18/67—Unsaturated compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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Abstract
The invention provides a kind of aqueous polyurethane acrylate copolymer emulsion and preparation method thereof.The aqueous polyurethane acrylate copolymer emulsion is first using diisocyanate, flame-proof polyol, non-flame resistant polyalcohol, the chain extender containing acidic-group, hydroxy acrylate and end-capping reagent as raw material; the phosphorous aqueous polyurethane emulsion containing carbon-carbon double bond is prepared by the method for chemical graft; again under the protection of phosphate ester surfactant; emulsion polymerization is carried out using acrylate, the phosphate of carbon-carbon double bonds, vinyl silicone oil, vinyl silicane coupling agent, acrylic crosslinking agent as raw material, is prepared.The aqueous polyurethane acrylate copolymer emulsion that the present invention is provided has higher solid content, dries that the used time is few, and its dried product has good fire resistance and heat decomposition resistance.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of aqueous polyurethane acrylate copolymer emulsion and its preparation
Method.
Background technology
Aqueous polyurethane (PUD) emulsion and water-and acrylate (PA) emulsion are current a large amount of widely used two classes high scores
Sub- material, has been widely used the base-material for making coating, ink, adhesive.Wherein, PUD emulsions there is excellent lower temperature resistance, it is wear-resisting
Property and solvent resistance, but stability is poor, solid content is low and cost is high；The characteristics of PA emulsions are maximum is exactly that cost is low, and hardness height,
Modificationization approach is more, solid content is relatively high, but haves the shortcomings that obvious " hot sticky cold crisp ".PUD and PA respectively have feature, by two
Person's copolymerization formed aqueous polyurethane acrylate (PUA) copolymer emulsion combine both advantages, at present increasingly by
Pay attention to and be widely used in furniture, papermaking, the industry such as building.
Due to containing polyurethane in PUA emulsions, the extremely toxic substances such as cyanide, therefore work can be produced during its film forming product burns
Had higher requirements in industry for its fire resistance.Moreover, temperature can often reach more than 300 DEG C in big fire, it is now most of
Polyurethane and polyacrylate material can also thermally decompose in itself, therefore, except anti-flammability, having for PUA latex products is resistance to
It is hot also to have much room for improvement.
CN 1597739A disclose a kind of new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material
And its synthesis technique, but it is not related to the improvement to emulsion anti-flammability and heat resistance.CN 105238245A disclose a kind of ring
Resin modified aqueous polyurethane anti-flaming dope of oxygen and preparation method thereof, by the film of the coating preparation, not only hardness is high, and
Good flame retardation effect, but it is to obtain fire resistance by the small molecule such as additional APP, melamine fire retardant, these
Small molecule fire retardant is noxious material, easily migrates to film coated surface, is detrimental to health.CN 1760224A disclose one kind
The preparation method of inflaming retarding type copolymerization latex of urethane acrylate, has synthesized a kind of polyurethane propylene having from flame retardant effect
Acid ester copolymer, and cold amalgamation part vinylidene chloride/acrylate copolymer emulsion, obtain flame-retardant polyurethane acrylate and are total to
Poly- emulsion.But its cold mixed vinylidene chloride/acrylate copolymer emulsion contains the fire-retardant composition of halogen, can produce bioxin and
The toxic gases such as halogen acids；And vinylidene chloride/there is phase between acrylate copolymer emulsion and urethane acrylate copolymer
Hold the problem of stability is poor；It introduces anti-flammability structure in polyurethane, limited from fire resistance；In addition, the PUA copolymerization
The solid content of emulsion is relatively low, and is not related to the improvement to heat decomposition resistance.
Therefore, a kind of watersoluble polyurethane acrylic acid with high solids content, anti-flammability and heat decomposition resistance how is obtained
Ester copolymer emulsion, is this area urgent problem to be solved.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the invention to provide a kind of aqueous polyurethane acrylate copolymerization
Emulsion and preparation method thereof.The aqueous polyurethane acrylate copolymer emulsion has higher solid content, its dried product
With good fire resistance and heat resistance.
For up to this purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of aqueous polyurethane acrylate copolymer emulsion, and its preparing raw material includes such as the following group
Point：
Component A, including：10-60wt% (such as 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%,
40wt%, 45wt%, 50wt%, 55wt% or 60wt% etc.) diisocyanate, 10-75wt% (such as 10wt%,
15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%,
70wt% or 75wt% etc.) flame-proof polyol, 0-75wt% (such as 0wt%, 2wt%, 5wt%, 8wt%, 10wt%,
15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%,
70wt% or 75wt% etc.) non-flame resistant polyalcohol, 3-8wt% (3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%,
5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt% or 8wt% etc.) the chain extender containing acidic-group, 1.5-18wt%
(such as 1.5wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%,
12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt% or 18wt% etc.) hydroxy acrylate and 0.5-
10wt% (such as 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%,
8wt%, 9wt% or 10wt% etc.) end-capping reagent；
Nertralizer, the nertralizer neutral and alkali group accounts for acidic-group mole in the chain extender containing acidic-group
90-150%；
Account for the component A gross mass 0-8% (such as 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7% or 8%)
Small molecule chain extender；
Account for the component A gross mass 25-400% (such as 25%, 50%, 75%, 100%, 125%, 150%, 175%,
200%th, 225%, 250%, 275%, 300%, 325%, 350%, 375% or 400% etc.) B component, the B component bag
Include：20-75wt% (such as 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%,
60wt%, 65wt%, 70wt% or 75wt% etc.) acrylate monomer, 10-50wt% (such as 10wt%, 15wt%,
20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% or 50wt% etc.) carbon-carbon double bonds phosphate, 5-
30wt% (such as 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%,
28wt% or 30wt% etc.) vinyl silicone oil, 1-5wt% (such as 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%,
3.5wt%, 4wt%, 4.5wt% or 5wt% etc.) vinyl silicane coupling agent and 1-4wt% (such as 1wt%, 1.5wt%,
2wt%, 2.5wt%, 3wt%, 3.5wt% or 4wt% etc.) crosslinking agent；
And account for the B component gross mass 1-5% (such as 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%,
4.5% or 5% etc.) phosphate ester surfactant and 0.1-1% (such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%,
0.6%th, 0.7%, 0.8%, 0.9% or 1% etc.) initiator.
Material synthesis aqueous polyurethane acrylate copolymer emulsion of the invention by using phosphor-containing flame-proof, by flame retarding construction
It is introduced into strand, imparts fire resistance in emulsion.Due to the flame-proof polyol in the component A of synthesis of polyurethane, containing acidity
The carbon-carbon double bonds in phosphorous raw material, and the B component of synthesis polyacrylate may be selected in the chain extender and end-capping reagent of group
Phosphate can have a higher addition, therefore improve the overall phosphorus content of aqueous polyurethane acrylate copolymer emulsion,
Make its dried product that there is good fire resistance.B component is the primary raw material of synthesis polyacrylate, passes through vinyl silicon
Oil, vinyl silicane coupling agent and crosslinking agent three cooperate, and crosslink strand and introduce organosilicon, so as to improve
The heat resistance of aqueous polyurethane acrylate copolymer emulsion.
As the preferred technical solution of the present invention, the B component accounts for the 50-200% of the component A gross mass.
As the preferred technical solution of the present invention, the diisocyanate is selected from toluene di-isocyanate(TDI) (TDI), different Fo Er
Ketone diisocyanate (IPDI), methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexyl
Methane diisocyanate (H12MDI), xylylene diisocyanate (XDI) or tetramethyl xylylene diisocyanate
(TMXDI) one kind or at least two combination in；For example can be TDI and IPDI combination, TDI and MDI combination, TDI
With HDI combination, TDI and H12MDI combination, TDI and XDI combination, IPDI and MDI combination, IPDI and HDI combination,
IPDI and H12MDI combination, IPDI and XDI combination, MDI and HDI combination or HDI and XDI combination etc..
Preferably, the flame-proof polyol is phosphoric acid ester polyalcohol.
Preferably, the phosphoric acid ester polyalcohol be selected from phosphoric acid ester PPG, phosphoric acid ester PEPA or
One kind or at least two combination in phosphoric acid ester polyether-polyester polyol.
Preferably, the non-flame resistant polyalcohol is selected from polyether Glycols, polyester diol, PCDL, polybutadiene
Enediol, polycaprolactone glycol, polymerized thylene carbonate ester polyol or one kind or at least two group in polyacrylate polyol
Close；For example can be polyether Glycols with the combination of polyester diol, the combining of PCDL and polybutadiene diol, gather
The combination of butadiene glycol and polycaprolactone glycol or the combination of polycaprolactone glycol and polyacrylate polyol etc..
Preferably, the polyether Glycols are polytetrahydrofuran diol.
As the preferred technical solution of the present invention, the chain extender containing acidic-group is selected from dihydroxymethyl phosphoric acid, dihydroxy
One kind or at least two in methylpropanoic acid (DMPA), dimethylolpropionic acid (DMBA), tartaric acid or dihydric alcohol containing Sulfonic acid structures
The combination planted；For example can be combination, dihydroxymethyl phosphoric acid and the dihydroxymethyl fourth of dihydroxymethyl phosphoric acid and dihydromethyl propionic acid
The combination of acid, the combination of dihydroxymethyl phosphoric acid and tartaric acid, combination, the dihydroxymethyl of dihydromethyl propionic acid and dimethylolpropionic acid
The combination of propionic acid and tartaric acid or the combination of tartaric acid and the dihydric alcohol containing Sulfonic acid structures etc..
Preferably, the hydroxy acrylate is selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, first
One kind or at least two combination in base hydroxy-ethyl acrylate, hydroxy propyl methacrylate or methacrylate；Example
Such as can be combination, hydroxy-ethyl acrylate and the hy-droxybutyl of hydroxy-ethyl acrylate and hydroxypropyl acrylate combination, third
Combination, the combination of hydroxypropyl acrylate and hydroxy propyl methacrylate or the propylene of olefin(e) acid hydroxyl ethyl ester and hydroxyethyl methacrylate
Combination of sour hydroxy butyl ester and methacrylate etc..
Preferably, the end-capping reagent is the phosphate containing monohydroxy.
Preferably, the phosphate containing monohydroxy is 2- ethoxys dimethyl phosphate and/or methylol diethyl phosphate.
As the preferred technical solution of the present invention, the nertralizer is selected from ammoniacal liquor, sodium hydroxide, potassium hydroxide, triethylamine
Or one kind in tri-n-butylamine or at least two combination；For example can be combination, ammoniacal liquor and the hydrogen-oxygen of ammoniacal liquor and sodium hydroxide
Change the group of combination, the combination of ammoniacal liquor and triethylamine, sodium hydroxide and the combination of triethylamine or sodium hydroxide and the tri-n-butylamine of potassium
Close etc..
Preferably, the small molecule chain extender is selected from ethylenediamine, IPD, hexamethylene diamine, piperazine, hydrazine hydrate, two
One kind or at least two combination in ethene triamine or triethylene tetramine；For example can be ethylenediamine and IPD
Combination, the combination of ethylenediamine and hexamethylene diamine, the combination of ethylenediamine and piperazine, combination, the ethylenediamine and two of ethylenediamine and hydrazine hydrate
The combination of ethene triamine, the combination of IPD and piperazine, combination or the isophorone of IPD and hydrazine hydrate
Combination of diamines and triethylene tetramine etc..
As the preferred technical solution of the present invention, the acrylate monomer is selected from methyl acrylate, ethyl acrylate, third
Olefin(e) acid N-butyl, isobutyl acrylate, Isooctyl acrylate monomer, isobornyl acrylate, styrene, methyl styrene, methyl-prop
One kind or at least two combination in e pioic acid methyl ester, EMA or n-BMA；For example can be
Combination, the combination of methyl acrylate and n-butyl acrylate, methyl acrylate and the propylene of methyl acrylate and ethyl acrylate
The combination of sour isobornyl thiocyanoacetate, the combination of methyl acrylate and EMA, ethyl acrylate and isobutyl acrylate
Combination, ethyl acrylate and the combination of Isooctyl acrylate monomer or the combination of ethyl acrylate and methyl methacrylate etc..
Preferably, the phosphate of the carbon-carbon double bonds is 2- hydroxy ethyl methyls acrylated phosphate and/or French sieve
The PAM-300 of Di Ya companies.
Preferably, the vinyl silicone oil at least one end is ethenyl blocking.
Preferably, viscosity of the vinyl silicone oil at 25 DEG C is 10-1000cp；For example can be 10cp, 20cp,
50cp, 100cp, 200cp, 300cp, 400cp, 500cp, 600cp, 700cp, 800cp, 900cp or 1000cp etc..
Preferably, the vinyl silicane coupling agent is selected from VTES (A-151), vinyl trimethoxy
Base silane (A-171), vinyl three ('beta '-methoxy ethyoxyl) silane (A-172), methacryloxypropyl trimethoxy
Silane (A-174) or one kind in vinyl silane triisopropoxide (KH-1706) or at least two combination；For example can be
A-151 and A-171 combination, A-151 and A-172 combination, A-151 and A-174 combination, A-151 and KH-1706 group
Combination, A-171 and KH-1706 combination or A-172 and KH-1706 combination of conjunction, A-171 and A-174 etc..
Preferably, the crosslinking agent is selected from NMA (NMA), hydroxyethyl acrylamide (HEAA), diacetone
Acrylamide (DAAM)/adipic dihydrazide (ADH), isobutoxymethyl acrylamide (IBMA) or methacrylic acid acetyl second
One kind or at least two combination in acyloxy ethyl ester (AAEM)；For example can be NMA and HEAA combination, NMA and IBMA
Combination, NMA and DAAM/ADH combination, HEAA and IBMA combination, HEAA and DAAM/ADH combination, HEAA and AAEM
Combination of combination, IBMA and AAEM etc..
It should be noted that " DAAM/adipic dihydrazide " in the present invention refers to by diacetone acrylamide
The crosslinking agent that acid amides is cooperatively formed with adipic dihydrazide, the two mutual cooperation can just play a part of crosslinking.
As the preferred technical solution of the present invention, the phosphate ester surfactant is response type or non-reactive phosphoric acid
Esters surface active agent；
Preferably, the response type phosphate ester surfactant is Shanghai Ai Dike Fine Chemical Co., Ltd
REASOAP PP-70；
Preferably, the non-reactive phosphate ester surfactant is selected from the graceful Chemical Co., Ltd. of Nanjing Hensel
EMPIPHOS DF1313, the EMPIPHOS DF1326 of the graceful Chemical Co., Ltd. of Nanjing Hensel, the limited public affairs of the graceful chemical industry of Nanjing Hensel
EMPIPHOS A5D, the PS-440E of Shanghai Ai Dike Fine Chemical Co., Ltd or Shanghai Ai Dike fine chemistry industries of department are limited
One kind or at least two combination in company PS-810E.
Response type phosphate ester surfactant can equally improve the phosphorus in aqueous polyurethane acrylate copolymer emulsion
Content, further improves its fire resistance.
Preferably, the initiator is selected from potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, hydrogen peroxide/sulfurous acid
Sodium, t-butyl hydroperoxide/ascorbic acid or one kind in potassium peroxydisulfate/sodium hydrogensulfite or at least two combination.
It should be noted that the form of " oxidant/reducing agent " refers to redox initiation system in the present invention, such as
" hydrogen peroxide/sodium sulfite " is the redox initiation system of hydrogen peroxide and sodium sulfite.
On the other hand, the present invention provides a kind of preparation method of above-mentioned aqueous polyurethane acrylate copolymer emulsion, including
Following steps：
(1) diisocyanate of formula ratio, flame-proof polyol and non-flame resistant polyalcohol are mixed, carries out polymerisation, instead
After answering completely, the chain extender containing acidic-group for adding formula ratio carries out chain extending reaction, obtains polyurethane prepolymer I；
(2) the polyurethane prepolymer I and formula ratio hydroxy acrylate are reacted, after reaction completely, added
The end-capping reagent of formula ratio carries out end capping reaction, obtains polyurethane prepolymer II；
(3) the polyurethane prepolymer II is neutralized with the nertralizer of formula ratio, then adds the third of 50-100% formula ratios
Olefin(e) acid ester monomer is swelled, and obtains polyurethane prepolymer III；
(4) the polyurethane prepolymer III is added to the water and disperseed, optionally small molecule chain extension is added after phase in version
Agent carries out chain extending reaction, obtains aqueous polyurethane emulsion；
(5) disperseed in the aqueous solution that the aqueous polyurethane emulsion is added to phosphate ester surfactant, then
Add remaining acrylate monomer, the phosphate of the carbon-carbon double bonds of formula ratio, vinyl silicone oil, vinyl silicane coupling agent
Pre-emulsification is carried out with crosslinking agent, pre-emulsion is formed, finally by initiator initiated polymerization, obtains the aqueous polyurethane third
Olefin(e) acid ester copolymer emulsion.
Using nertralizer and the acidic-group reaction forming salt in polyurethane prepolymer II, Neng Gouti in above-mentioned steps (3)
Its high hydrophily；Using acrylate monomer polyurethane prepolymer II is swelled instead of organic solvent, it is to avoid using having
The problem of its hydrophily declines is easily caused during machine solvent；Step (4) is scattered by the way that polyurethane prepolymer III is added to the water,
Easily occur phase in version, form the oil-in-water type micelle of big small particle, reduce water requirement；Phosphate ester surfactant is helped
The two alternate compatibilities in improvement emulsion.Each step cooperates, so as to make obtained aqueous polyurethane acrylate copolymerization
Emulsion has higher solid content.
It should be noted that " optionally " meaning that small molecule chain extender can be added in above-mentioned steps (4), it can not also add
Plus.When without small molecule chain extender, chain extending reaction can also occur in the presence of water for polyurethane prepolymer III.
As the preferred technical solution of the present invention, the preparation method also includes pre-treatment step：It is right before step (1)
Water removal is dried in the flame-proof polyol and non-flame resistant polyalcohol.The present invention is not limited the method for drying water removal, example
Property, the method for being dried in vacuo 1-3h at 100-140 DEG C can be selected to be removed water.
Preferably, the temperature of polymerisation described in step (1) is 70-100 DEG C, for example can be 70 DEG C, 72 DEG C, 75
DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 85 DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 95 DEG C, 98 DEG C or 100 DEG C etc.；Time is 2-4h, for example can be with
It is 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h or 4h etc..
Preferably, the temperature of chain extending reaction described in step (1) is 60-90 DEG C, for example can be 60 DEG C, 62 DEG C, 65 DEG C,
68 DEG C, 70 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 85 DEG C, 88 DEG C or 90 DEG C etc.；Time is 1.5-3h, for example, can be
1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h or 3h etc..
Preferably, the temperature of the reaction of polyurethane prepolymer I and hydroxy acrylate described in step (2) is 60-90 DEG C,
It for example can be 60 DEG C, 62 DEG C, 65 DEG C, 68 DEG C, 70 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 85 DEG C, 88 DEG C or 90 DEG C
Deng；Time is 30-60min, such as can be 30min, 35min, 40min, 45min, 50min, 55min or 60min.
Preferably, the temperature of end capping reaction described in step (2) is 60-80 DEG C, for example can be 60 DEG C, 62 DEG C, 65 DEG C,
68 DEG C, 70 DEG C, 72 DEG C, 75 DEG C, 78 DEG C or 80 DEG C etc.；Time is 30-60min, for example can be 30min, 35min, 40min,
45min, 50min, 55min or 60min etc..
Preferably, the temperature of the neutralization reaction in step (3) is less than 40 DEG C, and the time is 10-30min；For example can be
10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min or 30min etc..
Preferably, the temperature of chain extending reaction described in step (4) is 0-40 DEG C, for example can be 0 DEG C, 5 DEG C, 10 DEG C, 15
DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C or 40 DEG C etc.；Time is 30-60min, for example can be 30min, 35min, 40min,
45min, 50min, 55min or 60min etc..
Preferably, the pre-emulsified time described in step (5) is 30-60min；For example can be 30min, 35min,
40min, 45min, 50min, 55min or 60min etc..
Preferably, the temperature of polymerisation described in step (5) is 40-60 DEG C；For example can be 40 DEG C, 42 DEG C, 45 DEG C,
48 DEG C, 50 DEG C, 52 DEG C, 55 DEG C, 58 DEG C or 60 DEG C etc..
Preferably, the method for polymerisation is described in step (5)：By 3-10% (such as 3%, 4%, 5%, 6%,
7%th, 8%, 9% or 10% etc.) the pre-emulsion is mixed with remaining phosphate ester surfactant, adds 30-50%
The initiator of (such as 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38% or 40%) formula ratio, at 40-60 DEG C
Reacted under (such as 40 DEG C, 42 DEG C, 45 DEG C, 48 DEG C, 50 DEG C, 52 DEG C, 55 DEG C, 58 DEG C or 60 DEG C) to emulsion and become blue, continue anti-
Opened after answering 15-30min (such as 15min, 18min, 20min, 22min, 24min, 25min, 26min, 28min or 30min)
Begin that remaining pre-emulsion and initiator is added dropwise, dripped with 2-5h (such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h)
Finish, be further continued for reaction 0.5-1.5h (such as 0.5h, 0.6h, 0.8h, 1h, 1.2h, 1.4h or 1.5h).
As the preferred technical solution of the present invention, the preparation method comprises the following steps：
(1) flame-proof polyol and non-flame resistant polyalcohol are dried after water removal, mixed with the diisocyanate of formula ratio,
2-4h is reacted at 70-100 DEG C, the chain extender containing acidic-group of formula ratio is then added, 1.5-3h is reacted at 60-90 DEG C,
Obtain polyurethane prepolymer I；
(2) hydroxy acrylate of the polyurethane prepolymer I and formula ratio is reacted into 30-60min at 60-90 DEG C,
Then the end-capping reagent of formula ratio is added, 30-60min is reacted at 60-80 DEG C, obtains polyurethane prepolymer II；
(3) nertralizer of formula ratio, the neutralization reaction 10- below 40 DEG C are added into the polyurethane prepolymer II
30min, the acrylate monomer for then adding 50-100% formula ratios is swelled, and obtains polyurethane prepolymer III；
(4) the polyurethane prepolymer III is added to the water and disperseed, optionally small molecule chain extension is added after phase in version
Agent, reacts 30-60min at 0-40 DEG C DEG C, obtains aqueous polyurethane emulsion；
(5) disperseed in the aqueous solution that the aqueous polyurethane emulsion is added to phosphate ester surfactant, then
Add remaining acrylate monomer, the phosphate of the carbon-carbon double bonds of formula ratio, vinyl silicone oil, vinyl silicane coupling agent
Pre-emulsification 30-60min is carried out with crosslinking agent, pre-emulsion is formed, then by the 3-10% pre-emulsion and remaining phosphorus
Esters of gallic acid surfactant is mixed, and adds the initiator of 30-50% formula ratios, is reacted at 40-60 DEG C to emulsion and is become blue, continued
After reaction 15-30min start that remaining pre-emulsion and initiator is added dropwise, use 2-5h completion of dropping, be further continued for reacting 0.5-
1.5h, obtains the aqueous polyurethane acrylate copolymer emulsion.
The present invention is not limited for the method for salary distribution of phosphate ester surfactant in above-mentioned steps (5), this area skill
Art personnel can be selected according to actual needs, but should ensure that the total amount of phosphate ester surfactant is equal to formula ratio.
Compared with prior art, the invention has the advantages that：
Material synthesis aqueous polyurethane acrylate copolymer emulsion of the invention by using phosphor-containing flame-proof, by flame retarding construction
It is introduced into strand, imparts fire resistance in emulsion.The overall phosphorus content of emulsion is higher, with good anti-flammability.It is done
The fire endurance (GB 14907-2002) of dry product reaches 2.5-3h.
Polymerisation is participated in by using vinyl silicone oil, vinyl silicane coupling agent and crosslinking agent, molecule interchain is sent out
It is raw to be crosslinked and introduce organosilicon, so as to improve the heat resistanceheat resistant resolution of aqueous polyurethane acrylate copolymer emulsion dried product
Power.Thermal weight loss test is carried out to the dried product of aqueous polyurethane acrylate copolymer emulsion that the present invention is provided, it starts point
The temperature of solution is 220-230 DEG C, and temperature when weightless 60% is 245-265 DEG C.
The aqueous polyurethane acrylate copolymer emulsion water requirement that the present invention is provided is less, and its solid content can reach 55-
58%.
Embodiment
Technical scheme is further illustrated below by specific embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
Phosphoric acid ester polyester diol in the embodiment of the present invention is the BY3009T of the source Chemical Co., Ltd. of Beijing one hundred, end
Hydroxy silicon oil is the SPS-70 of the source Chemical Co., Ltd. of Beijing one hundred.
Embodiment 1
A kind of aqueous polyurethane acrylate copolymer emulsion, its preparing raw material is as follows：
The preparation method of above-mentioned aqueous polyurethane acrylate copolymer emulsion comprises the following steps：
(1) flame-proof polyol is dried in vacuo 2h at 120 DEG C, mixed by formula with diisocyanate, it is anti-at 90 DEG C
2h is answered, the chain extender containing acidic-group of formula ratio is then added, reacts 1.5h at 75 DEG C, obtain polyurethane prepolymer I；
(2) above-mentioned polyurethane prepolymer I and formula ratio hydroxy acrylate are reacted into 45min, Ran Houjia at 75 DEG C
Enter the end-capping reagent of formula ratio, 60min is reacted at 60 DEG C, obtain polyurethane prepolymer II；
(3) above-mentioned polyurethane prepolymer II is cooled to less than 40 DEG C, adds the nertralizer of formula ratio, neutralization reaction
10min, then adds the acrylate monomer of formula ratio, stirs, obtain polyurethane prepolymer III；
(4) above-mentioned polyurethane prepolymer III is added to the water in 3min, entered under normal temperature under 4000r/min rotating speed
Row high speed shearing emulsification 30min, obtains aqueous polyurethane emulsion；
(5) divided in the aqueous solution that above-mentioned aqueous polyurethane emulsion is added to the phosphate ester surfactant containing 1.2kg
Dissipate, phosphate, vinyl silicone oil, vinyl silicane coupling agent and the crosslinking agent for then adding the carbon-carbon double bonds of formula ratio are carried out
Pre-emulsification 30min, forms pre-emulsion, then mixes 5% above-mentioned pre-emulsion and remaining phosphate ester surfactant
Close, add the initiator of 50% formula ratio, react blue to emulsion change at 60 DEG C, continuation is reacted starts that residue is added dropwise after 15min
Pre-emulsion and initiator, use 2h completion of dropping, be further continued for insulation reaction 1h, after cooling filter, obtain above-mentioned aqueous poly- ammonia
Ester acrylate copolymer emulsion.
Embodiment 2
A kind of aqueous polyurethane acrylate copolymer emulsion, its preparing raw material is as follows：
The preparation method of above-mentioned aqueous polyurethane acrylate copolymer emulsion comprises the following steps：
(1) flame-proof polyol is dried in vacuo 2h at 120 DEG C, mixed by formula with diisocyanate, it is anti-at 80 DEG C
3h is answered, the chain extender containing acidic-group of formula ratio is then added, reacts 3h at 60 DEG C, obtain polyurethane prepolymer I；
(2) above-mentioned polyurethane prepolymer I and formula ratio hydroxy acrylate are reacted into 30min, Ran Houjia at 90 DEG C
Enter the end-capping reagent of formula ratio, 30min is reacted at 80 DEG C, obtain polyurethane prepolymer II；
(3) above-mentioned polyurethane prepolymer II is cooled to less than 40 DEG C, adds the nertralizer of formula ratio, neutralization reaction
20min, then adds the acrylate monomer of formula ratio, stirs, obtain polyurethane prepolymer III；
(4) above-mentioned polyurethane prepolymer III is added to the water in 3min, entered under normal temperature under 5000r/min rotating speed
Row high speed shearing emulsification 60min, obtains aqueous polyurethane emulsion；
(5) divided in the aqueous solution that above-mentioned aqueous polyurethane emulsion is added to the phosphate ester surfactant containing 1.9kg
Dissipate, phosphate, vinyl silicone oil, vinyl silicane coupling agent and the DAAM for then adding the carbon-carbon double bonds of formula ratio are carried out in advance
60min is emulsified, pre-emulsion is formed, then mixes 3% above-mentioned pre-emulsion with remaining phosphate ester surfactant,
The initiator of 30% formula ratio is added, is reacted at 40 DEG C to emulsion and becomes blue, it is remaining pre- to start dropwise addition after continuation reaction 30min
Emulsion and initiator, use 5h completion of dropping, are further continued for insulation reaction 1h, and it is 7.5 that pH is adjusted after cooling, adds ADH 2.4kg
Stir filtering, obtains above-mentioned aqueous polyurethane acrylate copolymer emulsion.
Embodiment 3
A kind of aqueous polyurethane acrylate copolymer emulsion, its preparing raw material is as follows：
The preparation method of above-mentioned aqueous polyurethane acrylate copolymer emulsion comprises the following steps：
(1) flame-proof polyol is dried in vacuo 2h at 120 DEG C, mixed by formula with diisocyanate, it is anti-at 70 DEG C
4h is answered, the chain extender containing acidic-group of formula ratio is then added, reacts 1.5h at 90 DEG C, obtain polyurethane prepolymer I；
(2) above-mentioned polyurethane prepolymer I and formula ratio hydroxy acrylate are reacted into 60min, Ran Houjia at 60 DEG C
Enter the end-capping reagent of formula ratio, 45min is reacted at 70 DEG C, obtain polyurethane prepolymer II；
(3) above-mentioned polyurethane prepolymer II is cooled to less than 40 DEG C, adds the nertralizer of formula ratio, neutralization reaction
10min, then adds the acrylate monomer of formula ratio, stirs, obtain polyurethane prepolymer III；
(4) above-mentioned polyurethane prepolymer III is added to the water in 3min, entered under normal temperature under 3000r/min rotating speed
Row high speed shearing emulsification, then adds the small molecule chain extender of formula ratio, reacts 45min, obtains aqueous polyurethane emulsion；
(5) disperseed in the aqueous solution that above-mentioned aqueous polyurethane emulsion is added to phosphoric acid esters surface active agent, so
Phosphate, vinyl silicone oil, vinyl silicane coupling agent and the crosslinking agent for adding the carbon-carbon double bonds of formula ratio afterwards carry out pre- breast
Change 30min, form pre-emulsion, then take 10% above-mentioned pre-emulsion, the initiator of 50% formula ratio is added, at 50 DEG C
Reaction to emulsion becomes blue, continues after reacting 20min to start that remaining pre-emulsion and initiator is added dropwise, uses 4h completion of dropping, then
Continue insulation reaction 0.5h, filtered after cooling, obtain above-mentioned aqueous polyurethane acrylate copolymer emulsion.
Embodiment 4
A kind of aqueous polyurethane acrylate copolymer emulsion, its preparing raw material is as follows：
The preparation method of above-mentioned aqueous polyurethane acrylate copolymer emulsion is same as Example 3.
Embodiment 5
A kind of aqueous polyurethane acrylate copolymer emulsion, its preparing raw material is as follows：
The preparation method of above-mentioned aqueous polyurethane acrylate copolymer emulsion is same as Example 3.
Comparative example 1
With differing only in for embodiment 1, the consumption of vinyl silicone oil is 10.4kg, vinyl silicane coupling agent and crosslinking
The consumption of agent is 0.
Comparative example 2
With differing only in for embodiment 1, the consumption of vinyl silicane coupling agent is 10.4kg, vinyl silicone oil and crosslinking
The consumption of agent is 0.
Comparative example 3
With differing only in for embodiment 1, the consumption of crosslinking agent is 10.4kg, vinyl silicone oil and vinyl silanes coupling
The consumption of agent is 0.
The solid content for the aqueous polyurethane acrylate copolymer emulsion that measure above-described embodiment 1-5 and comparative example 1-3 is provided,
Particle diameter and Storage period, and film is prepared into, fire resistance and heat resistance are determined, it is as a result as shown in table 1 below.
Table 1
From the data of upper table 1, when not adopting the cooperation of vinyl silicone oil, vinyl silicane coupling agent and crosslinking agent,
The heat resistance of obtained aqueous polyurethane acrylate copolymer emulsion is poor, and 170-180 DEG C begins to thermal decomposition, 210-220 DEG C
When weight loss just reach 60%, heat resistance is poor.The present invention cooperates by using three, improves aqueous polyurethane third
The heat resistance of olefin(e) acid ester copolymer emulsion film.
Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention
In the technical scope of dew, the change or replacement that can be readily occurred in, within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of aqueous polyurethane acrylate copolymer emulsion, it is characterised in that the watersoluble polyurethane acrylic acid copolymer emulsion
Preparing raw material include following component：
Component A, including：10-60wt% diisocyanate, 10-75wt% flame-proof polyol, 0-75wt% it is non-flame resistant many
First alcohol, the 3-8wt% chain extender containing acidic-group, 1.5-18wt% hydroxy acrylate and 0.5-10wt% end-blocking
Agent；
Nertralizer, the nertralizer neutral and alkali group accounts for the 90- of acidic-group mole in the chain extender containing acidic-group
150%；
Account for the small molecule chain extender of the component A gross mass 0-8%；
The B component of the component A gross mass 25-400% is accounted for, the B component includes：20-75wt% acrylate monomer,
The phosphate of 10-50wt% carbon-carbon double bonds, 5-30wt% vinyl silicone oil, 1-5wt% vinyl silicane coupling agent
With 1-4wt% crosslinking agent；
And account for the phosphate ester surfactant of the B component gross mass 1-5% and 0.1-1% initiator.
2. aqueous polyurethane acrylate copolymer emulsion according to claim 1, it is characterised in that the B component accounts for institute
State the 50-200% of component A gross mass.
3. aqueous polyurethane acrylate copolymer emulsion according to claim 1 or 2, it is characterised in that two isocyanide
Acid esters is selected from toluene di-isocyanate(TDI), IPDI, methyl diphenylene diisocyanate, the isocyanide of hexa-methylene two
In acid esters, dicyclohexyl methyl hydride diisocyanate, xylylene diisocyanate or tetramethyl xylylene diisocyanate
It is a kind of or at least two combination；
Preferably, the flame-proof polyol is phosphoric acid ester polyalcohol；
Preferably, the phosphoric acid ester polyalcohol is selected from phosphoric acid ester PPG, phosphoric acid ester PEPA or phosphoric acid
One kind or at least two combination in esters polyether-polyester polyol；
Preferably, the non-flame resistant polyalcohol is selected from polyether Glycols, polyester diol, PCDL, polybutadiene two
Alcohol, polycaprolactone glycol, polymerized thylene carbonate ester polyol or one kind in polyacrylate polyol or at least two combination；
Preferably, the polyether Glycols are polytetrahydrofuran diol.
4. the aqueous polyurethane acrylate copolymer emulsion according to any one of claim 1-3, it is characterised in that described
Chain extender containing acidic-group is selected from dihydroxymethyl phosphoric acid, dihydromethyl propionic acid, dimethylolpropionic acid, tartaric acid or knot containing sulfonic acid
One kind or at least two combination in the dihydric alcohol of structure, preferably dihydroxymethyl phosphoric acid；
Preferably, the hydroxy acrylate is selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, methyl-prop
One kind or at least two combination in olefin(e) acid hydroxyl ethyl ester, hydroxy propyl methacrylate or methacrylate；
Preferably, the end-capping reagent is the phosphate containing monohydroxy；
Preferably, the phosphate containing monohydroxy is 2- ethoxys dimethyl phosphate and/or methylol diethyl phosphate.
5. the aqueous polyurethane acrylate copolymer emulsion according to any one of claim 1-4, it is characterised in that described
The combination of the one kind or at least two of nertralizer in ammoniacal liquor, sodium hydroxide, potassium hydroxide, triethylamine or tri-n-butylamine；
Preferably, the small molecule chain extender is selected from ethylenediamine, IPD, hexamethylene diamine, piperazine, hydrazine hydrate, divinyl
One kind or at least two combination in triamine or triethylene tetramine.
6. the aqueous polyurethane acrylate copolymer emulsion according to any one of claim 1-5, it is characterised in that described
Acrylate monomer be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, Isooctyl acrylate monomer,
Isobornyl acrylate, styrene, methyl styrene, methyl methacrylate, EMA or methacrylic acid are just
One kind or at least two combination in butyl ester；
Preferably, the phosphate of the carbon-carbon double bonds be 2- hydroxy ethyl methyls acrylated phosphate and/or French sieve it is sub-
The PAM-300 of company；
Preferably, the vinyl silicone oil at least one end is ethenyl blocking；
Preferably, viscosity of the vinyl silicone oil at 25 DEG C is 10-1000cp；
Preferably, the vinyl silicane coupling agent is selected from VTES, vinyltrimethoxy silane, ethene
Base three ('beta '-methoxy ethyoxyl) silane, methacryloxypropyl trimethoxy silane or vinyl silane triisopropoxide
In one kind or at least two combination；
Preferably, the crosslinking agent is selected from NMA, hydroxyethyl acrylamide, DAAM/adipic acid
One kind or at least two group in two hydrazides, isobutoxymethyl acrylamide or acetoacetoxyethyl methacrylate
Close.
7. the aqueous polyurethane acrylate copolymer emulsion according to any one of claim 1-6, it is characterised in that described
Phosphate ester surfactant is response type or non-reactive phosphate ester surfactant；
Preferably, the response type phosphate ester surfactant is the REASOAP of Shanghai Ai Dike Fine Chemical Co., Ltd
PP-70；
Preferably, the non-reactive phosphate ester surfactant is selected from the EMPIPHOS of the graceful Chemical Co., Ltd. of Nanjing Hensel
DF1313, the EMPIPHOS DF1326 of the graceful Chemical Co., Ltd. of Nanjing Hensel, Nanjing Hensel graceful Chemical Co., Ltd.
EMPIPHOS A5D, the REASOAP PP-70 of Shanghai Ai Dike Fine Chemical Co., Ltd, Shanghai Ai Dike fine chemistry industries are limited
The PS-440E of company or one kind in the PS-810E of Shanghai Ai Dike Fine Chemical Co., Ltd or at least two combination；
Preferably, the initiator is selected from potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, hydrogen peroxide/sodium sulfite, mistake
The hydrogen oxide tert-butyl group/ascorbic acid or one kind in potassium peroxydisulfate/sodium hydrogensulfite or at least two combination.
8. the preparation method of the aqueous polyurethane acrylate copolymer emulsion according to any one of claim 1-7, it is special
Levy and be, the preparation method comprises the following steps：
(1) diisocyanate of formula ratio, flame-proof polyol and non-flame resistant polyalcohol are mixed, carries out polymerisation, reacted
Quan Hou, the chain extender containing acidic-group for adding formula ratio carries out chain extending reaction, obtains polyurethane prepolymer I；
(2) the polyurethane prepolymer I and formula ratio hydroxy acrylate are reacted, after reaction completely, adds formula
The end-capping reagent of amount carries out end capping reaction, obtains polyurethane prepolymer II；
(3) the polyurethane prepolymer II is neutralized with the nertralizer of formula ratio, then adds the acrylic acid of 50-100% formula ratios
Ester monomer is swelled, and obtains polyurethane prepolymer III；
(4) the polyurethane prepolymer III is added to the water and disperseed, optionally small molecule chain extender is added after phase in version and is entered
Row chain extending reaction, obtains aqueous polyurethane emulsion；
(5) disperseed in the aqueous solution that the aqueous polyurethane emulsion is added to phosphate ester surfactant, then added
Remaining acrylate monomer, the phosphate of the carbon-carbon double bonds of formula ratio, vinyl silicone oil, vinyl silicane coupling agent and friendship
Join agent and carry out pre-emulsification, form pre-emulsion, finally by initiator initiated polymerization, obtain the watersoluble polyurethane acrylic acid
Ester copolymer emulsion.
9. preparation method according to claim 8, it is characterised in that the preparation method also includes pre-treatment step：
Water removal is dried to the flame-proof polyol and non-flame resistant polyalcohol before step (1)；
Preferably, the temperature of polymerisation described in step (1) is 70-100 DEG C, and the time is 2-4h；
Preferably, the temperature of chain extending reaction described in step (1) is 60-90 DEG C, and the time is 1.5-3h；
Preferably, the temperature of the reaction of polyurethane prepolymer I and hydroxy acrylate described in step (2) is 60-90 DEG C, time
For 30-60min；
Preferably, the temperature of end capping reaction described in step (2) is 60-80 DEG C, and the time is 30-60min；
Preferably, the temperature of the neutralization reaction in step (3) is less than 40 DEG C, and the time is 10-30min；
Preferably, the temperature of chain extending reaction described in step (4) is 0-40 DEG C, and the time is 30-60min；
Preferably, the pre-emulsified time described in step (5) is 30-60min；
Preferably, the temperature of polymerisation described in step (5) is 40-60 DEG C；
Preferably, the method for polymerisation is described in step (5)：By the 3-10% pre-emulsion and remaining phosphate
Class surfactant is mixed, and adds the initiator of 30-50% formula ratios, is reacted at 40-60 DEG C to emulsion and is become blue, continues to react
Start that remaining pre-emulsion and initiator is added dropwise after 15-30min, use 2-5h completion of dropping, be further continued for reacting 0.5-1.5h.
10. preparation method according to claim 8 or claim 9, it is characterised in that the preparation method comprises the following steps：
(1) flame-proof polyol and non-flame resistant polyalcohol are dried after water removal, mixed with the diisocyanate of formula ratio, in 70-100
2-4h is reacted at DEG C, the chain extender containing acidic-group of formula ratio is then added, reacts 1.5-3h at 60-90 DEG C, gathered
Urethane prepolymer I；
(2) the polyurethane prepolymer I and formula ratio hydroxy acrylate are reacted into 30-60min at 60-90 DEG C, then
The end-capping reagent of formula ratio is added, 30-60min is reacted at 60-80 DEG C, obtains polyurethane prepolymer II；
(3) into the polyurethane prepolymer II add formula ratio nertralizer, the neutralization reaction 10-30min below 40 DEG C, so
The acrylate monomer for adding 50-100% formula ratios afterwards is swelled, and obtains polyurethane prepolymer III；
(4) the polyurethane prepolymer III is added to the water and disperseed, optionally small molecule chain extender is added after phase in version,
30-60min is reacted at 0-40 DEG C, aqueous polyurethane emulsion is obtained；
(5) disperseed in the aqueous solution that the aqueous polyurethane emulsion is added to phosphate ester surfactant, then added
Remaining acrylate monomer, the phosphate of the carbon-carbon double bonds of formula ratio, vinyl silicone oil, vinyl silicane coupling agent and friendship
Join agent and carry out pre-emulsification 30-60min, pre-emulsion is formed, then by the 3-10% pre-emulsion and remaining phosphate
Class surfactant is mixed, and adds the initiator of 30-50% formula ratios, is reacted at 40-60 DEG C to emulsion and is become blue, continues to react
Start that remaining pre-emulsion and initiator is added dropwise after 15-30min, use 2-5h completion of dropping, be further continued for reacting 0.5-1.5h, obtain
To the aqueous polyurethane acrylate copolymer emulsion.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760224A (en) * | 2005-09-29 | 2006-04-19 | 上海申真企业发展有限公司 | Method for preparing inflaming retarding type copolymerization latex of urethane acrylate |
| CN102153712A (en) * | 2010-12-17 | 2011-08-17 | 北京天维宝辰化学产品有限公司 | Water-based polyurethane-acrylate emulsion and re-dispersible latex powder prepared from same |
| CN102702450A (en) * | 2012-05-22 | 2012-10-03 | 电子科技大学中山学院 | Preparation method of waterborne polyurethane-acrylate emulsion |
-
2017
- 2017-07-25 CN CN201710613842.8A patent/CN107286306B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760224A (en) * | 2005-09-29 | 2006-04-19 | 上海申真企业发展有限公司 | Method for preparing inflaming retarding type copolymerization latex of urethane acrylate |
| CN102153712A (en) * | 2010-12-17 | 2011-08-17 | 北京天维宝辰化学产品有限公司 | Water-based polyurethane-acrylate emulsion and re-dispersible latex powder prepared from same |
| CN102702450A (en) * | 2012-05-22 | 2012-10-03 | 电子科技大学中山学院 | Preparation method of waterborne polyurethane-acrylate emulsion |
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