CN107698731A - The high rigidity acroleic acid polyurethane emulsion that a kind of POSS/B is modified - Google Patents
The high rigidity acroleic acid polyurethane emulsion that a kind of POSS/B is modified Download PDFInfo
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Abstract
The present invention relates to the high rigidity acroleic acid polyurethane emulsion that a kind of POSS/B is modified, its preparation method is：Using oligomer polyol, boronic acid derivatives, isocyanate-monomer elder generation synthesis modification polyurethane, add cross-linking type acrylic acid monomer, six acrylate-based POSS the alcohol chain extender under catalyst action and synthesize POSS/B acroleic acid polyurethane performed polymers, the high rigidity acroleic acid polyurethane emulsion of described POSS/B modifications is synthesized finally by neutralization, emulsification, amine chainextender etc..The high rigidity acroleic acid polyurethane emulsion that a kind of POSS/B produced by the present invention is modified, with high rigidity and bin stability, manufactured film has excellent adhesive force, wearability, water resistance, resistance to ag(e)ing, stain resistance, pliability, corrosion resistance and from anti-flammability.
Description
Technical field
The present invention relates to a kind of acrylic acid-polyurethane emulsion, more particularly to the high rigidity propylene that a kind of POSS/B is modified
Acid-polyaminoester emulsion, belong to water-base resin technical field.
Technical background
Severe environmental regulation has been formulated in succession both at home and abroad has been discharged to limit VOC (VOC) to air,
High-performance, environmental protection have turned into the direction of paint development.The synthesis of polyurethane resin is by traditional solvent-borne type hydrotropism's polyurethane
Transformation, aqueous polyurethane coating have pollution-free, safe and reliable, good mechanical performance, compatibility is good, is easy to using water as solvent
It is the advantages that modified, famous with its durability and chemical resistance, in woodcare paint field with car paint field because its is excellent
Performance, favored by user.
But polyaminoester emulsion is present, and solid content is smaller, film formation time is long, coating can the shortcoming such as burning-point is low, in patent and article
Delivered in the presence of a large amount of relevant modified aqueous polyurethane researchs with what is applied.
Chinese patent CN105461863A discloses a kind of acrylic ester modified water-soluble polyurethane emulsion and preparation method thereof,
Aqueous polyurethane is modified using acrylate, the polyurethane material of excellent combination property is obtained, is joined using acrylate
Double bond is incorporated into polyurethane backbone with reacting, then triggers the polymerization of acrylic monomers, the network structure of complexity can be formed,
For the traditional waterborne polyurethane that compares, water resistance, heat resistance, mechanical property are significantly improved.
On the other hand, as the improvement of people's living standards, flame-retardant architectural paint, fire-retardant veneer coating are by consumer's
Welcome.Chinese patent CN105238245A discloses aqueous polyurethane anti-flaming dope and its preparation side of a kind of epoxy resin modification
Method, reach coating flame-retardant standard by adding fire retardant, its advantage is that not only hardness of film is high, resistance to for aqueous polyurethane anti-flaming dope
It is water-based good, and its fire resistance period is long, smoke amount is few, good flame resistance, nontoxic.But due to add ammonium polyphosphate flame retardant,
The small molecule such as melamine and pentaerythrite, soluble compound or nuisance, therefore fire retardant be present and be easily free on coating table
Face, the shortcomings of fire-retardant timeliness is short, coating is harmful.
The content of the invention
A kind of the present invention is intended to provide high rigidity acrylic acid-polyurethane emulsion that POSS/B is modified and preparation method thereof.
POSS is also known as cage modle polysilsesquioxane, the inorganic kernel being made up of the Si-O silica skeletons alternately connected, its
Shape is for example same " cage ", belongs to Nano compound.Diversity, high activity and the preferable polymer-compatible of POSS groups
Property is allowed to by physical blending but also can not only be introduced into polymeric material by the method for chemical copolymerization.
The POSS polymer-modified surface smoothness that can significantly improve polymeric material, wearability, the transparency and pliability；
Eight arm configurations using POSS and the functional group with reactivity and high symmetry, the resin of preparation is a kind of star tree
Dendritic polymer, higher crosslink density is obtained, improve the compactness, water resistance and hardness of film.
The high rigidity acrylic acid-polyurethane emulsion that POSS/B of the present invention is modified, is in acrylic acid-polyurethane molecule
Boronic acid derivatives and six acrylate-based POSS are introduced in structure so that in acrylic acid-polyurethane molecular skeleton containing boron oxygen key,
Silicon oxygen bond, there is star dendritic structure, effectively improve the water resistance of acrylic emulsion, self-cleaning, wearability, corrosion resistance and
Anti-flammability.
The shortcomings that to overcome prior art and deficiency, the present invention take following technical scheme, and a kind of described POSS/B changes
The high rigidity acrylic acid-polyurethane emulsion of property, is counted, its composition is in parts by weight：10.0~20.0 parts of oligomer polyols,
6.0~12.0 parts of boronic acid derivatives, 30.0~40.0 parts of isocyanate-monomers, 5.0~10.0 parts of cross-linking type acrylic acid monomers,
5.0~10.0 part of six acrylate-based POSS, 1.0~3.0 parts of catalyst, 0.02~0.5 part of initiator, 2.0~10.0 parts of alcohol
Chain extender, 2.0~5.0 parts of triethylamines, 1.0~3.0 parts of amine chainextenders, 100.0~180.0 parts of deionized waters.
Wherein, described oligomer polyol is PEPA or PPG；Described PEPA is poly-
At least one of tetramethylene adipate dihydric alcohol, PCDL or polycaprolactone diols, Mn be 1000~
3000；Described PPG is in PTMG, polytetramethylene ether diol or polyoxypropylene glycol
At least one, Mn be 1000~3000.
Described boronic acid derivatives are triethyl borate, trimethylborate, triisopropyl borate ester, phenylboric acid, 3- fluorobenzene
Ylboronic acid, sec-butyl boric acid, 4- flurophenyl boronic acids, 3- methoxyphenyl-boronic acids, n-Butaneboronic acid, 2- methoxyphenyl-boronic acids,
Phenethyl boric acid, to ethyl phenyl boric acid, 2- fluorine pyridine -3- boric acid, 4- bromobenzeneboronic acids, 4- chlorophenylboronic acids, n-propyl boric acid, 4- just
At least one of propyl group phenyl boric acid or pcarboxyphenylboronic acid.
Described isocyanate-monomer is at least one of HDI, MDI, IPDI or HMDI.
Described catalyst is alkalinous metal carboxylate, organo-metallic compound, phosphorus-containing compound or amine；Further
, preferably dibutyl tin laurate, lithium acetate, three normal-butyl phosphorus, stannous octoate, aphthenic acids tin, lead naphthenate, aphthenic acids
At least one of cobalt, dibutyitin maleate or dibutyltin diacetate.
Described cross-linking type acrylic acid monomer is N- hydroxyethyl acrylamides, N hydroxymethyl acrylamide or N- hydroxypropyls third
At least one of acrylamide.
Six described acrylate-based POSS, its molecular structural formula are as follows：
Described initiator is at least one of ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.
Described alcohol chain extender is ethylene glycol, 1,2- propane diols, 1,4- butanediols, 1,6-HD, 1,5- pentanediols, three
At least one of hydroxymethyl-propane, neopentyl glycol or glycol.
Described amine chainextender is at least one of ethylenediamine, diethylenetriamine, hexamethylene diamine or piperazine.
The high rigidity acrylic acid-polyurethane emulsion that described POSS/B is modified, its preparation method are as follows：
A) POSS/B- acrylic acid modified polyurethane performed polymers, are synthesized：By 10.0~20.0 parts of oligomer polyols, 6.0~
12.0 parts of boronic acid derivatives, 30.0~40.0 parts of isocyanate-monomers, 1.0~3.0 parts of catalyst are added in reactor, lead to N2
Protection, under the stirring of 300~600rpm rotating speeds, it is warming up to 80~100 DEG C of 1~2h of reaction；Then 5.0~10.0 parts are added dropwise dropwise
The mixed liquor of cross-linking type acrylic acid monomer, 5.0~10.0 part of six acrylate-based POSS and 0.02~0.1 part of initiator, keep
Continue 1~3h of reaction at 80~100 DEG C；60~80 DEG C are cooled to, adds 20.0~30.0 parts of solvent dilution regulation system viscosity,
Add 2.0~10.0 parts of alcohol chain extenders, 0.02~0.1 part of catalyst continues 1~3h of reaction, obtain described POSS/B- propylene
Sour modified polyurethane prepolymer；
B) acrylic acid-polyurethane emulsion of POSS/B modifications, is prepared：By described POSS/B- acrylic acid modified polyurethanes
Performed polymer cools to 35~45 DEG C, adds 2.0~5.0 parts of nertralizer triethylamines, stirs 5~10min；It is subsequently added into 80.0~
150.0 parts of deionized waters, in the emulsified 15~30min of 1000~1200rpm high speeds；Then dripped under 300~500rpm low speed
Add 20.0~45.0 parts of 2.5~13.0% amine chainextender aqueous solution, be added dropwise in 15~30min, holding chain extending reaction 1~
2h, solvent is then evaporated under reduced pressure out, obtains the acrylic acid-polyurethane emulsion that described POSS/B is modified.
Wherein, described solvent is at least one of acetone, butanone, cyclohexanone.
2.5~13.0% described amine chainextender aqueous solution：1.0~3.0 parts of amine chainextenders are dissolved in 20.0~40.0
In the deionized water of part.
The high rigidity acrylic acid-polyurethane emulsion that a kind of POSS/B produced by the present invention is modified, has high rigidity and storage
Stability, manufactured film have excellent adhesive force, wearability, water resistance, resistance to ag(e)ing, stain resistance, pliability, corrosion resistant
Corrosion and from anti-flammability.
Embodiment
A kind of POSS/B of present invention high rigidity acrylic acid-polyurethane emulsions being modified are done into one with reference to embodiment
The description of step.It is understood that specific embodiment described herein is used only for explaining related invention, rather than to the invention
Restriction.
Embodiment 1
The high rigidity acrylic acid-polyurethane emulsion that a kind of POSS/B is modified, is prepared by following steps：
A) POSS/B- acrylic acid modified polyurethane performed polymers, are synthesized：By 20.0 parts of poly adipate succinic acid ester dihydric alcohols
(Mn1000), 12.0 parts of trimethylborates, 32.0 parts of MDI, 2.0 parts of dibutyl tin laurates are added in reactor, lead to N2
Protection, under the stirring of 500rpm rotating speeds, it is warming up to 95 DEG C of reaction 1.6h；Then dropwise be added dropwise 8.0 parts of N- hydroxyethyl acrylamides,
The mixed liquor of 6.0 part of six acrylate-based POSS and 0.1 part of ammonium persulfate, it is maintained at 80 DEG C and continues to react 3h；60 DEG C are cooled to,
Add 30.0 parts of butanone dilution regulation system viscosity, add 6.0 parts of BDOs, 0.04 part of dibutyl tin laurate after
Continuous reaction 2h, obtains described POSS/B- acrylic acid modified polyurethane performed polymers；
B) acrylic acid-polyurethane emulsion of POSS/B modifications, is prepared：Acrylic acid-poly- ammonia that described POSS/B is modified
Ester performed polymer cools to 35 DEG C, adds 4.0 parts of nertralizer triethylamines, stirs 10min；130.0 parts of deionized waters are subsequently added into,
The emulsified 25min of 1200rpm high speeds；Then 7.5% 27.0 parts of the diethylenetriamine aqueous solution is added dropwise under 300rpm low speed,
It is added dropwise in 30min, keeps chain extending reaction 1.8h, be then evaporated under reduced pressure out solvent butanone, obtains the POSS/B is modified third
Olefin(e) acid-polyaminoester emulsion.
Embodiment 2
The high rigidity acrylic acid-polyurethane emulsion that a kind of POSS/B is modified, is prepared by following steps：
A) POSS/B- acrylic acid modified polyurethane performed polymers, are synthesized：By 10.0 parts of polyoxypropylene glycol
(Mn1500), 6.0 parts are added in reactor to ethyl phenyl boric acid, 40.0 parts of IPDI, 3.0 parts of cobalt naphthenates, lead to N2Protection,
Under the stirring of 300rpm rotating speeds, 80 DEG C of reaction 2h are warming up to；Then dropwise be added dropwise 10.0 parts of N hydroxymethyl acrylamides, 5.0 part six
The mixed liquor of acrylate-based POSS and 0.02 part of potassium peroxydisulfate, it is maintained at 80 DEG C and continues to react 3h；60 DEG C are cooled to, is added
30.0 parts of acetone dilute regulation system viscosity, add 2.0 parts of 1,6- hexylene glycols, 0.02 part of cobalt naphthenate continues to react 3h, obtain
Described POSS/B- acrylic acid modified polyurethane performed polymers；
B) acrylic acid-polyurethane emulsion of POSS/B modifications, is prepared：Acrylic acid-poly- ammonia that described POSS/B is modified
Ester performed polymer cools to 45 DEG C, adds 2.0 parts of nertralizer triethylamines, stirs 5min；120.0 parts of deionized waters are subsequently added into,
The emulsified 10min of 1200rpm high speeds；Then 7.0% 43.0 parts of the diethylenetriamine aqueous solution is added dropwise under 200rpm low speed,
It is added dropwise in 10min, keeps chain extending reaction 1h, be then evaporated under reduced pressure out solvent acetone, obtains the propylene that the POSS/B is modified
Acid-polyaminoester emulsion.
Embodiment 3
The high rigidity acrylic acid-polyurethane emulsion that a kind of POSS/B is modified, is prepared by following steps：
A) POSS/B- acrylic acid modified polyurethane performed polymers, are synthesized：By 12.4 parts of polycaprolactone diolss (Mn3000),
10.5 parts of sec-butyl boric acid, 36.0 parts of HMDI, 1.8 parts of dibutyitin maleates are added in reactor, lead to N2Protection,
Under the stirring of 450rpm rotating speeds, 92 DEG C of reaction 1.5h are warming up to；Then dropwise be added dropwise 8.5 parts of N hydroxymethyl acrylamides, 8.0 part six
The mixed liquor of acrylate-based POSS and 0.05 part of ammonium persulfate, it is maintained at 92 DEG C and continues to react 2.5h；80 DEG C are cooled to, is added
28.0 parts of acetone dilute regulation system viscosity, add 6.0 parts of neopentyl glycols, 0.05 part of dibutyitin maleate continues to react
2.5h, obtain described POSS/B- acrylic acid modified polyurethane performed polymers；
B) acrylic acid-polyurethane emulsion of POSS/B modifications, is prepared：Acrylic acid-poly- ammonia that described POSS/B is modified
Ester performed polymer cools to 40 DEG C, adds 4.0 parts of nertralizer triethylamines, stirs 10min；120.0 parts of deionized waters are subsequently added into,
The emulsified 20min of 1000rpm high speeds；Then 4.0% 37.5 parts of the hexamethylene diamine aqueous solution is added dropwise under 400rpm low speed,
It is added dropwise in 20min, keeps chain extending reaction 1.5h, be then evaporated under reduced pressure out solvent acetone, obtains the POSS/B is modified third
Olefin(e) acid-polyaminoester emulsion.
The high rigidity acrylic acid-polyurethane emulsion that POSS/B in the embodiment of the present invention is modified, its technical indicator such as institute of table 1
Show：
The POSS of table 1 is modified high rigidity water resistance alkyd resin technical indicator
| Solid content | Viscosity | Glass transition temperature Tg | |
| Embodiment 1 | 36.8% | 355±10mPa·s | 45℃ |
| Embodiment 2 | 33.5% | 320±10mPa·s | 42℃ |
| Embodiment 3 | 36.0% | 315±10mPa·s | 47℃ |
The emulsion of embodiments of the invention is configured to aqueous fire-proof coating and self-flame-retardant acrylic acid fireproof on the market
Coating (comparative example) carries out performance contrast test, is detected according to relevant criterion, its test data is as shown in table 2：
The water-based self-flame-retardant coating property technical indicator of table 2
Although the present invention has been explained in detail and refer to embodiment, for one of ordinary skill in the art, show
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of claim.
Claims (9)
- A kind of 1. high rigidity acrylic acid-polyurethane emulsion that POSS/B is modified, it is characterised in that the height that described POSS/B is modified Hardness acrylic acid-polyurethane emulsion, is counted in parts by weight, and its composition is：10.0~20.0 parts of oligomer polyols, 6.0~ 12.0 parts of boronic acid derivatives, 30.0~40.0 parts of isocyanate-monomers, 5.0~10.0 parts of cross-linking type acrylic acid monomers, 5.0~ 10.0 part of six acrylate-based POSS, 1.0~3.0 parts of catalyst, 0.02~0.5 part of initiator, 2.0~10.0 parts of alcohol chain extensions Agent, 2.0~5.0 parts of triethylamines, 1.0~3.0 parts of amine chainextenders, 100.0~180.0 parts of deionized waters；Wherein, six described acrylate-based POSS, its molecular structural formula are as follows：Described boronic acid derivatives are triethyl borate, trimethylborate, triisopropyl borate ester, phenylboric acid, 3- fluorophenyl boron Acid, sec-butyl boric acid, 4- flurophenyl boronic acids, 3- methoxyphenyl-boronic acids, n-Butaneboronic acid, 2- methoxyphenyl-boronic acids, benzene second Ylboronic acid, to ethyl phenyl boric acid, 2- fluorine pyridine -3- boric acid, 4- bromobenzeneboronic acids, 4- chlorophenylboronic acids, n-propyl boric acid or 4- positive third At least one of base phenyl boric acid or pcarboxyphenylboronic acid；Described isocyanate-monomer is at least one of HDI, MDI, IPDI or HMDI；Described cross-linking type acrylic acid monomer For at least one of N- hydroxyethyl acrylamides, N hydroxymethyl acrylamide or N- hydroxypropylacrylamides.
- 2. the high rigidity acrylic acid-polyurethane emulsion that POSS/B according to claim 1 is modified, it is characterised in that described Oligomer polyol be PEPA or PPG；Described PEPA is poly adipate succinic acid ester binary At least one of alcohol, PCDL or polycaprolactone diols, Mn are 1000~3000；Described PPG For at least one of PTMG, polytetramethylene ether diol or polyoxypropylene glycol, Mn is 1000~ 3000。
- 3. the high rigidity acrylic acid-polyurethane emulsion that POSS/B according to claim 1 is modified, it is characterised in that described Catalyst be alkalinous metal carboxylate, organo-metallic compound, phosphorus-containing compound or amine.
- 4. the high rigidity acrylic acid-polyurethane emulsion that POSS/B according to claim 1 is modified, it is characterised in that described Catalyst for dibutyl tin laurate, lithium acetate, three normal-butyl phosphorus, stannous octoate, aphthenic acids tin, lead naphthenate, cycloalkanes At least one of sour cobalt, dibutyitin maleate or dibutyltin diacetate.
- 5. the high rigidity acrylic acid-polyurethane emulsion that POSS/B according to claim 1 is modified, it is characterised in that described Initiator at least one of for ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.
- 6. the high rigidity acrylic acid-polyurethane emulsion that POSS/B according to claim 1 is modified, it is characterised in that described Alcohol chain extender for ethylene glycol, 1,2- propane diols, 1,4- butanediols, 1,6-HD, 1,5- pentanediols, trimethylolpropane, At least one of neopentyl glycol or diethylene glycol (DEG)；Described amine chainextender is in ethylenediamine, diethylenetriamine, hexamethylene diamine or piperazine At least one.
- 7. a kind of preparation method for the high rigidity acrylic acid-polyurethane emulsion that POSS/B according to claim 1 is modified, its It is characterised by, step is as follows：A) POSS/B- acrylic acid modified polyurethane performed polymers, are synthesized：By 10.0~20.0 parts of oligomer polyols, 6.0~12.0 Part boronic acid derivatives, 30.0~40.0 parts of isocyanate-monomers, 1.0~3.0 parts of catalyst are added in reactor, lead to N2Protect Shield, under the stirring of 300~600rpm rotating speeds, it is warming up to 80~100 DEG C of 1~2h of reaction；Then 5.0~10.0 parts of friendships are added dropwise dropwise The mixed liquor of connection type acrylic monomers, 5.0~10.0 part of six acrylate-based POSS and 0.02~0.1 part of initiator, is maintained at 80~100 DEG C are continued 1~3h of reaction；60~80 DEG C are cooled to, adds 20.0~30.0 parts of solvent dilution regulation system viscosity, then 2.0~10.0 parts of alcohol chain extenders of addition, 0.02~0.1 part of catalyst continue 1~3h of reaction, obtain described POSS/B- acrylic acid Modified polyurethane prepolymer；B) acrylic acid-polyurethane emulsion of POSS/B modifications, is prepared：By described POSS/B- acrylic acid modified polyurethane pre-polymerizations Body cools to 35~45 DEG C, adds 2.0~5.0 parts of nertralizer triethylamines, stirs 5~10min；It is subsequently added into 80.0~150.0 Part deionized water, in the emulsified 15~30min of 1000~1200rpm high speeds；Then 2.5 are added dropwise under 300~500rpm low speed ~13.0% 20.0~45.0 parts of the amine chainextender aqueous solution, is added dropwise in 15~30min, keeps 1~2h of chain extending reaction, so After be evaporated under reduced pressure out solvent, obtain the acrylic acid-polyurethane emulsion that described POSS/B is modified.
- 8. the high rigidity acrylic acid-polyurethane emulsion that POSS/B according to claim 7 is modified, it is characterised in that described Solvent be acetone, butanone, at least one of cyclohexanone.
- 9. the high rigidity acrylic acid-polyurethane emulsion that POSS/B according to claim 7 is modified, it is characterised in that described 2.5~13.0% amine chainextender aqueous solution, 1.0~3.0 parts of amine chainextenders are dissolved in 20.0~40.0 parts of deionized water In.
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| CN115490864A (en) * | 2022-09-29 | 2022-12-20 | 长兴化学（天津）有限公司 | POSS hybrid waterborne polyurethane emulsion and preparation method and application thereof |
| CN115490864B (en) * | 2022-09-29 | 2023-08-15 | 长兴化学（天津）有限公司 | POSS hybridized waterborne polyurethane emulsion and preparation method and application thereof |
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