CN110452490B - Dual POSS polyether hybrid water-based acrylic resin dispersion, preparation method and composition for preparing resin coating film - Google Patents
Dual POSS polyether hybrid water-based acrylic resin dispersion, preparation method and composition for preparing resin coating film Download PDFInfo
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Abstract
The invention discloses a double POSS polyether hybrid water-based acrylic resin dispersion and a preparation method thereof, wherein a lipophilic polymerizable acrylate monomer, a non-ester monomer and a water-soluble functional monomer, namely alkenyl polyether carboxylic acid are polymerized under the action of a free radical initiator to generate a polymer surfactant with self-emulsifying capacity; then, under the action of the surfactant and a free radical initiator, the acrylic ester monomer, the non-ester monomer and the hydrophilic functional monomer which are physically hybridized by the double POSS polyether are subjected to free radical copolymerization, and then neutralization and phase inversion are carried out, so that the water-based acrylic ester resin dispersion POSSPA which is physically hybridized by the double POSS polyether is prepared, and the water-based acrylic ester resin dispersion POSSPA is compounded with a polyurethane crosslinking agent and then used for resin curing, so that the defects of poor gloss, fullness and the like of emulsion type acrylic ester resin due to the existence of an emulsifier can be overcome, and the performances of the resin coating such as hardness, heat resistance and the like can be improved.
Description
Technical Field
The invention belongs to the field of functional water-based resin, and particularly relates to a double POSS polyether hybrid polyacrylic resin and a preparation method thereof.
Background
Polyacrylate (PA) resin has good film forming property, strong adhesive force and easy curing, and a coating film prepared by the Polyacrylate (PA) resin has light color, high transparency, good luster, toughness and fullness, strong developing property and good weather resistance, and is popular as the most common matrix resin material. However, in recent years, due to environmental protection pressure and VOC emission, solvent-based PA resins and applications thereof have been greatly limited, and water-based or water-emulsion type acrylate resins (such as CN101914185) are favored because of economy, safety, environmental protection, and low odor. However, the aqueous polyacrylate resin prepared by the emulsion polymerization method has low gloss and poor water resistance, and is influenced by the surfactant or emulsifier used in the synthesis, and needs to be improved. Based on this, the system itself generates a high molecular surfactant through chemical reaction, then the water-resistant acrylic resin is emulsified, and then the resin is converted into water-based dispersion by using a phase inversion method under the condition of not adding additional surfactant (CN101914185, CN102408726, CN106832157), and the problem is hopefully solved.
In addition, hybrid modification of PA resins with oligomeric silsesquioxane POSS has been a research hotspot in the field of resin coatings in recent years, and the method not only can improve the flame retardancy and heat-resistant stability of PA resins, but also can contribute to the improvement of the hardness and physical and mechanical properties of resin coating films, as can be seen in documents CN 102757535, CN 103435741, CN 106215462 and the like. However, in the literature, most commonly used POSS for hybridizing acrylic resin is alkenyl-containing POSS, such as monomethacrylate-based POSS, octamethacrylate-based POSS, octavinyl POSS, etc., and whether to hybridize acrylic resin with bis-POSS polyether (i.e., bis-POSS-based polyoxyethylene polyoxypropylene ether) with a novel structure and improve the performance of PA resin by using the hybrid acrylic resin is not reported.
Disclosure of Invention
The invention aims to disclose a double POSS polyether hybrid water-based acrylic resin dispersion and a preparation method thereof. For this purpose, the invention firstly carries out free radical copolymerization on a lipophilic polymerizable monomer such as an acrylate monomer and a non-ester alkenyl monomer as well as a hydrophilic functional monomer under the action of a free radical initiator, and firstly synthesizes a high molecular polymer surfactant with dispersion and emulsification; then, initiating free radical copolymerization reaction of acrylic ester monomers and the like of double POSS polyether physical hybridization under the action of the surfactant, and then neutralizing and phase inversion to prepare double POSS polyether hybridization modified water-based acrylate resin dispersion POSSPA; when in use, the coating is crosslinked and cured by the curing agent, so that not only can a bright, transparent and plump coating be obtained, but also the hardness and the physical and mechanical properties of the coating can be beneficially improved.
The invention adopts the specific technical scheme that:
a double POSS polyether hybrid water-based acrylate resin and a preparation method thereof are characterized by comprising the following steps:
(1) firstly, sequentially weighing lipophilic polymerizable monomers such as acrylate monomers, non-ester alkenyl monomers and hydrophilic functional monomers G1 according to the mass ratio, mixing, and stirring and uniformly mixing to obtain a polymerizable monomer mixture A; dividing A into two parts, namely A1 and A2, wherein A1 accounts for about 10-30% of A by mass, and A2 accounts for about 70-90% of A by mass;
mixing A1 with water-soluble functional monomer G2, partial free radical initiator C1 and partial molecular weight regulator CTA1, stirring, mixing to obtain mixture B1, and placing in dropping funnel 1;
mixing A2 with double POSS polyether (DPPE for short, the synthesis method is referred to CN 109517312), ultrasonically dispersing and uniformly mixing, then adding a free radical initiator C2 and a molecular weight regulator CTA2, stirring and uniformly mixing, and placing the obtained mixture, namely B2, in another dropping funnel 2 for later use.
(2) Adding a solvent used for carrying out polymerization reaction into a three-necked bottle provided with a thermometer, a reflux condenser tube and a stirrer, stirring, heating to the set reaction temperature of 80-130 ℃, dropwise adding B1 while stirring, controlling the dropping time of B1 to be about 0.5-1h, and continuously carrying out heat preservation reaction for about 1h after the dropping is finished; then, dropwise adding B2 while stirring, controlling the dropwise adding time of B2 to be about 1-3h, after the dropwise adding of B2 is finished, and then carrying out heat preservation reaction at 80-130 ℃ for 1-2 h.
After the reaction is finished, stirring, cooling to 60-80 ℃, adding organic base with the same molar weight as that of the functional monomer G2 for neutralization for 10-20min, adjusting the pH value of the system to be about 6.0-7.5, then adding deionized water under the action of dispersion and stirring of a high-shear machine until the content (expressed by mass concentration) of the system resin is about 30-50%, and filtering to obtain water-based emulsion with blue fluorescence, namely the double POSS polyether hybrid water-based acrylate resin dispersion, which is recorded as POSSPA.
The oleophilic polymerizable acrylate monomer comprises two types of acrylate and methacrylate containing 1-8 carbon atoms, and is mainly selected from one or more of acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate (also known as isooctyl acrylate), cyclohexyl acrylate, isobornyl acrylate or methacrylate such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate (also known as isooctyl methacrylate), cyclohexyl methacrylate and isobornyl methacrylate;
the non-ester alkenyl monomer is mainly one of styrene, acrylonitrile and 4-chloromethyl styrene;
the hydrophilic functional monomer G1 is an acrylic acid derivative having hydroxyl group in its molecule, such as one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and N-methylolacrylamide, which can increase the water solubility of the resin produced by the system and can react with a subsequent curing agent, and the amount of the hydrophilic functional monomer G1 is preferably such that the hydroxyl value (expressed by the mass number of hydroxyl group contained per 100G of solid resin) of the resin produced by the system is maintained at 1.0-3.5%, more preferably 2.0-3.5%; in other words, G1 is used in an amount of about 12 to about 27% by weight of the total mass of the polymerizable monomers A + G2.
The mass of the lipophilic polymerizable monomer, namely acrylic ester monomer and non-ester alkenyl monomer accounts for 73-88% of the total mass of the polymerizable monomer A + G2, wherein the acrylic ester monomer accounts for 36.5-88% and the non-ester alkenyl monomer accounts for 0-44%;
the water-soluble functional monomer G2 is an alkenyl carboxylic acid compound which contains double bonds in molecules, has good reactivity with the monomer mixture A, can endow the polymer with good emulsifying performance after neutralization, and has the structure shown as formula (I) -1 and (I) -2, wherein a in the formula1、a2、b1、b2Is a non-negative integer such as 0,1,2,3 … …, preferably a1、a2、 b1、b2Is in the range of 0-30, and a1+b1、a2+b2The value range of (1) to (30); the alkenyl carboxylic acid with the structure shown as formula (I) -1 and (I) -2 is generally prepared by reacting hydroxyl-terminated allyl (poly) ether with maleic anhydride or succinic anhydride at a molar ratio of 1:1 at 70-125 ℃ for 1-4 h; the dosage of the G2 is 3-6% of the total mass of the polymerizable monomer A + G2.
CH2＝CHCH2O(C2H4O)a1(C3H6O)b1COCH2CH2COOH (I)-1
CH2＝CHCH2O(C2H4O)a2(C3H6O)b2COCH＝CHCOOH (I)-2
The free radical initiators C1 and C2, which may be the same or different, are generally substances that can release free radicals when being decomposed by heat and are mutually soluble with the monomer mixture A, and mainly comprise Azobisisobutyronitrile (AIBN), Benzoyl Peroxide (BPO), tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxycarbonate and the like, and the dosage of the free radical initiators C1 and C2 is 2-3.5% of the total mass of the monomer mixture A + G2. The C1 accounts for 10-35% of the total mass of C1+ C2, and the C2 accounts for 65-90% of the total mass of C1+ C2;
the molecular weight regulators CTA1 and CTA2, which may be the same or different, are typically alkyl mercaptans or other small molecular organic compounds containing mercapto groups, such as dodecyl mercaptan, mercaptoethanol or mercaptoacetic acid, and are used in an amount of 1-3.0% of the total mass of the polymerizable total monomers A + G2; the CTA1 accounts for about 10-30% of the total mass of the molecular weight regulator CTA1+ CTA2, and the CTA2 accounts for about 70-90% of the total mass of the molecular weight regulator CTA1+ CTA 2.
The structure of the Double POSS Polyether (DPPE) is shown as a formula (II), and semi-closed cage-shaped oligomeric silsesquioxane trisilicol T is used in a method of reference documents CN109517312 or CN1096088027(OH)3The polyether is prepared by low-temperature polycondensation with a hexafunctional silane coupling agent, namely alpha, omega-bis (trialkoxy silicon propyl) polyether, wherein R is one or more of isobutyl, isooctyl, octyl and phenyl, a and b are non-negative integers such as 0,1,2 and 3 … …, and the value range of a and b is preferably selected to be 3-25; the amount of the bis POSS polyether (DPPE) is about 5 to 25% of the total mass of the monomer mixture A + G2.
The solvent used for carrying out the resin polymerization reaction is mainly a small molecular alcohol, alcohol ether ester or ester solvent which has good intersolubility with the polymerizable monomer mixture A and the functional monomer G2, and the using amount of the solvent is generally 10-50% of the total mass of the polymerizable monomer A + G2; and depending on the boiling point and amount, the solvent may be removed or left in the bulk phase after the resin has been phase-inverted, for example by distillation under reduced pressure.
The polymerization reaction temperature is 80-130 ℃, and the reaction is implemented by adopting a mode of adding materials and reacting at the same time, and the specific operation is as follows: stirring and heating the solvent used for the polymerization reaction to 80-130 ℃, then dropwise adding B1 while stirring, controlling the dropping time of B1 to be 0.5-1h, and continuously preserving the heat at 80-130 ℃ for about 1h after the dropping is finished; then dropwise adding B2, controlling the dropwise adding time of B2 to be about 1-3h, after the dropwise adding of B2 is finished, and then preserving the heat at 80-130 ℃ for reacting for 1-2 h.
The organic base used in the neutralization reaction is one of N, N-dimethylaminoethanol, ethanolamine, diethanolamine, triethylamine and the like.
The invention has the beneficial effects that: in order to improve the influence of an emulsifier on the performance of acrylic resin in emulsion polymerization, the invention firstly carries out free radical copolymerization on part of lipophilic polymerizable monomers such as acrylic esters, non-ester monomers and the like and water-soluble functional monomers G2, and utilizes the difference of the ratio of the lipophilic monomers to the hydrophilic monomers to firstly prepare a polymer surfactant which contains a large amount of hydrophilic carboxylated (poly) ether groups in the molecule and has good emulsifying capacity; then, double POSS polyether with cage-shaped POSS suspended at two molecular ends is taken as an inorganic-organic nano hybrid component, the characteristic that organic groups and polyether groups in DPPE molecules have good intersolubility with polymerizable acrylate monomers and polymers thereof is fully utilized, the double POSS polyether is dissolved in a polymerizable monomer mixture A2 to prepare a homogeneous true solution, then polymerization reaction of the polymerizable monomers such as acrylate/non-ester monomers and functional monomers in the system is initiated under the combined action of a polymer surfactant and a free radical initiator generated by the system, the average molecular weight of the resin polymer is adjusted through mercaptan and the like, and high-temperature phase inversion is carried out, so that the water-based polyacrylic resin dispersion with water dispersivity and environmental protection is prepared, and the method not only can keep the characteristics of solvent-based PA resin such as high gloss, fullness, good developing property and the like, and the resin coating can be endowed with good hardness and heat-resistant stability by being matched with a curing agent.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Preparation of water-soluble functional monomer G2
Sequentially adding hydroxyl-terminated allyl hydroxyethyl ether or hydroxyl-terminated Allyl Polyether (APE) into a three-necked bottle provided with a thermometer, a reflux condenser tube and a stirrer, stirring, heating to 70-125 ℃, then adding Maleic Anhydride (MA) or Succinic Anhydride (SA) with the molar weight of 1-1.05 while stirring, and continuously controlling the temperature to 70-125 ℃ for reacting for 1-4h to obtain colorless-light yellow transparent liquid, namely water-soluble functional monomer G2-carboxylated allyl polyether (CPE). The starting materials and amounts used for the synthesis of G2 in the examples are specified in Table 1.
TABLE 1 raw materials and amounts used for the synthesis of functional monomer G2
APE1：a2＝1、b20, the product formula: CH (CH)2＝CHCH2OCH2CH2OCOCH＝CHCOOH；APE2： a1＝3、b1The product formula is 7: CH (CH)2＝CHCH2O(C2H4O)3(C3H6O)7COCH2CH2COOH；APE3：a1＝3、 b10, the product formula: CH (CH)2＝CHCH2O(C2H4O)3COCH2CH2COOH；APE4:a1＝10、b120, product formula: CH (CH)2＝CHCH2O(C2H4O)10(C3H6O)20COCH2CH2COOH; MA: maleic anhydride, Mn 98; and SA: succinic anhydride, Mn 100
Synthesis of (di) bis POSS polyether-bis POSS polyoxyethylene polyoxypropylene ether
The synthesis was carried out according to the methods of references CN109517312 or CN 109608802. That is, 0.01mol of semi-closed cage-like oligomeric silsesquioxane trisilicol [ T ] was weighed in a three-necked flask equipped with a thermometer, a reflux condenser and a stirrer7(OH)3]Dissolving with solvent to obtain dilute solution with mass concentration of 10-20%, stirring, and adding dropwise (CH) 0.005mol3O)3SiC3H6O(C2H4O)a(C3H6O)bC3H6Si(OCH3)3Alpha, omega-bis (trimethoxysilylpropyl) polyoxyethylene polyoxypropylene ether [ PECA, wherein a and b are the same as formula (II)]And a catalytic amount of an organotin catalyst (e.g., dibutyltin dilaurate), stirring until uniformAnd then controlling the temperature to be 0-10 ℃ to continuously perform polycondensation reaction for 24 hours, after the reaction is finished, evaporating the solvent under reduced pressure, and drying the product in vacuum to obtain the Double POSS Polyether (DPPE).
Example 1
(1) Weighing 27.75g of butyl acrylate, 20.00g of methyl methacrylate, 20.46g of styrene and 26.79g of hydroxypropyl acrylate HPAA in sequence according to the metering ratio, and uniformly stirring to obtain 95.00g of monomer mixture A; a is divided into two parts, A1 and A2, wherein A19.50g accounts for about 10% of A, A285.50g accounts for about 90% of A
Taking A1 and 5g as shown in formula (I) -2, a2＝1、b20, 200 and molecular formula CH2＝CHCH2OC2H4Mixing water-soluble functional monomer alkenyl carboxylic acid G2 of OCOCH ═ CHCOOH, 0.5G of free radical initiator di-tert-butyl peroxide (BuOOBuOOBu) and 0.2G of mercaptoethanol, stirring and mixing uniformly to obtain a total of 15.20G of a mixture, designated as B1, and placing in a dropping funnel 1 for later use;
a2 and 25g are also selected as shown in formula (II), R is i-C4H9Bis (heptaisobutyl POSS) polyoxypropylene ether (DPPE-1, as synthesized in example 1 of CN 109517312) (isobutyl), a-0, B-3, and a + B-3) were mixed, stirred, ultrasonically dispersed, then 3g of di-tert-butyl peroxide (BuOOBu) and 0.8g of mercaptoethanol were added, stirred, and mixed to obtain a mixture containing bis POSS polyether DPPE-1, designated B2, which was placed in another dropping funnel 2 for further use.
(2) Adding about 10G of ethylene glycol monobutyl ether (accounting for 10 percent of the total mass of A + G2) solvent used for carrying out polymerization reaction into a three-necked bottle provided with a thermometer, a reflux condenser tube and a stirrer, stirring, heating to 130 ℃, then dropwise adding B1 while stirring, controlling the dropping time to be about 0.5h, and continuing the heat preservation reaction for 1h after the dropping is finished so as to enable the system to generate a hydrophilic polymer surfactant for phase inversion; then, B2 was added dropwise while stirring, the dropping time of B2 was controlled to 1 hour, and the reaction was continued for 1 hour at 130 ℃.
After the reaction is finished, stirring, cooling to 80 ℃, adding about 2.23G N, N-dimethylethanolamine with the same molar weight as G2 for neutralization for 10min, wherein the pH value of the system is about 7.5, and then adding 121.73G of deionized water under the stirring action of a high-shear disperser with the rotation speed of 1000-1500r/min until the mass concentration of the system resin is about 50 percent to obtain white water-based emulsion with blue light, namely the double POSS polyether DPPE-1 hybrid water-based acrylate resin dispersoid which is marked as SPAPOS-1 and has the hydroxyl content of about 2.8 percent.
Example 2
(1) Weighing 20.7g of butyl methacrylate, 20.0g of ethyl acrylate, 40.60g of styrene and 12.7g of hydroxypropyl methacrylate in sequence according to the metering ratio, and uniformly stirring to obtain 94.0g of monomer mixture A; dividing A into two parts, namely A1 and A2, wherein A118.80g accounts for about 20 percent of the mass of A, A275.20g accounts for about 80 percent of the mass of A;
taking A1 and 6.0g as shown in formula (I) -1, a1＝3、b17, Mn 696, molecular formula CH2＝CHCH2O(C2H4O)3(C3H6O)7COCH2CH2Mixing a water-soluble functional monomer G2 of COOH, 0.6G of di-tert-butyl hydroperoxide BuOOH and 0.4G of thioglycolic acid, stirring and uniformly mixing to obtain a total 25.8G of mixture, which is marked as B1, and placing the mixture in a dropping funnel 1 for later use;
taking A2 and 5.0g as shown in formula (II), wherein R is i-C8H17Bis (heptaisooctyl POSS) polyoxyethylene polyoxypropylene ether (DPPE-2, as synthesized in example 3 of CN 109517312) of bis POSS polyether (isooctyl), a ═ 7, B ═ 3, and a + B ═ 10 were mixed, and after uniform ultrasonic dispersion, 1.4g of di-tert-butyl peroxide BuOOBu and 1.6g of thioglycolic acid were added, and after uniform stirring, the mixture containing bis POSS polyether DPPE-2, designated as B2, was placed in another dropping funnel 2 for use;
(2) adding 10.0G of propylene glycol butyl ether and 40.0G of propylene glycol methyl ether acetate (the total amount is 50.0G and accounts for about 50 percent of the total mass of the monomers A + G2) into a three-necked bottle provided with a thermometer, a reflux condenser and a stirrer, stirring, heating to 120 ℃, dropwise adding B1 while stirring, controlling the dropping time of B1 to be about 1 hour, and continuing to perform heat preservation reaction for 1 hour after dropping is finished so as to enable the system to generate a phase-transfer polymer surfactant; then, B2 was added dropwise while stirring, the dropping time of B2 was about 3 hours, and the reaction was continued by controlling the temperature at 120 ℃ for 2 hours after the dropping.
After the reaction is finished, cooling to 60 ℃, stirring, adding diethanolamine with the molar quantity equal to that of G2 and about 0.91G for neutralization for 20min to obtain the pH value of the system of about 6.0, and then adding 206.45G deionized water under the stirring action of a high-shear disperser with the rotation speed of 1000-1500r/min until the mass concentration of the system resin is about 30 percent to obtain white water-based emulsion with blue light, namely the double POSS polyether DPPE-2 hybrid water-based acrylate resin dispersion, which is recorded as POSSPA-2 and has the hydroxyl content of 1.43 percent.
Example 3
(1) Weighing 37.9g of tert-butyl methacrylate, 20.0g of cyclohexyl methacrylate, 13.0g of isoamyl acrylate, 7.0g of acrylonitrile and 19.1g of hydroxyethyl acrylate in sequence according to the metering ratio, and uniformly stirring to obtain 97.0g of monomer mixture A; dividing A into two parts, A1 and A2, wherein A1 is about 14.55g and accounts for 15% of A mass, A2 is about 82.45g and accounts for 85% of A mass;
taking A1 and 3.0g as shown in formula (I) -1, a1＝3、b10, 290 Mn and CH molecular formula2＝CHCH2O(C2H4O)3COCH2CH2Stirring and uniformly mixing a water-soluble functional monomer G2 of COOH, 0.6G of radical initiator Benzoyl Peroxide (BPO) and 0.4G of dodecanethiol to obtain a total 17.55G of mixture, recording as B1, and placing in a dropping funnel 1 for later use;
taking A2 and 10g as shown in formula (II), wherein R is i-C8H17Bis (heptaisooctyl POSS) polyoxyethylene polyoxypropylene ether (DPPE-3, see example 3 of CN109517312, iso-octyl), bis POSS polyether (iso-octyl), a ═ 7, b ═ 18, and a + b ═ 25Method synthesis), adding 1.9g of free radical initiator BPO and 1.1g of dodecanethiol after ultrasonic dispersion is uniform, stirring and uniformly mixing to obtain a mixture containing the bis POSS polyether DPPE-3, wherein the mixture is marked as B3, and placing the mixture in another dropping funnel 2 for later use;
(2) adding a mixed solvent (25G in total and 25% of the total mass of A + G2) consisting of 10G of butyl cellosolve and 15G of isopropanol into a three-necked bottle provided with a thermometer, a reflux condenser tube and a stirrer, stirring, heating to 80 ℃, then dropwise adding B1 while stirring, controlling the dropping time of B1 to be about 45min, and continuing to perform heat preservation reaction for 0.5h after the dropping is finished so as to enable the system to generate a phase transfer polymer surfactant; then, B2 was added dropwise while stirring, the dropping time of B2 was controlled to about 2 hours, and the reaction was continued for 2 hours at 80 ℃ after the dropping.
After the reaction is finished, stirring, cooling to 60 ℃, adding triethylamine with the same molar weight as G2 and about 1.05G for neutralization for 15min, wherein the pH value of the system is about 7.0, then adding 130.62G of deionized water and evaporating low-boiling-point alcohol solvent under the stirring action of a high-shear disperser with the rotation speed of 1000-1500r/min to obtain blue-light-carrying aqueous emulsion with the resin mass concentration of about 45 percent, namely the double POSS polyether DPPE-3 hybridized water-based acrylate resin dispersoid which is recorded as SPAPOS-3 and has the hydroxyl content of about 2.54 percent.
Example 4
(1) Weighing 25.0g of isooctyl methacrylate, 18.0g of butyl acrylate, 20.0g of methyl methacrylate, 12.8g of isobornyl methacrylate and 19.2g of hydroxyethyl methacrylate in sequence according to the metering ratio, and uniformly stirring to obtain 95.0g of monomer mixture A; dividing A into two parts, namely A1 and A2, wherein A is 128.5g and accounts for about 30% of A by mass, and A266.5g and accounts for about 70% of A by mass;
taking A1 and 5.0g as shown in formula (I) -1, a1＝10、b120, 1758 and CH molecular formula2＝CHCH2O(C2H4O)10(C3H6O)20COCH2CH2COOH water-soluble functional monomer G2, 1.0G initiator Azobisisobutyronitrile (AIBN) and 0.6G dodecanethiol, stirring and mixing uniformly, and placing the obtained mixture, marked as B1, in a dropping funnel 1 for later use;
taking A2 and 15g as shown in formula (II), wherein R is i-C4H9(isobutyl), a ═ 10, B ═ 10, a + B ═ 20 bis POSS polyether-bis (heptaisobutyl POSS) polyoxyethylene polyoxypropylene ether (DPPE-4, synthesis see CN109517312 example 4), mixing, after dispersing uniformly by ultrasound, adding 2.0g of free radical initiator AIBN and 2.4g of dodecanethiol, stirring and mixing, the resulting mixture, denoted as B2, was placed in another dropping funnel 2 for use;
(2) adding about 30G of propylene glycol dimethyl ether solvent (accounting for 30 percent of the total mass of A + G2) for polymerization into a three-necked bottle provided with a thermometer, a reflux condenser tube and a stirrer, stirring, heating to 90 ℃, then dropwise adding B1 while stirring, controlling the dropping time of B1 to be 1h, and continuing to perform heat preservation reaction for 35min after dropping is finished so as to enable the system to generate a phase-transfer polymer surfactant; then, B2 was added dropwise while stirring, the dropping time of B2 was 2 hours, and the reaction was continued at 90 ℃ for 1.5 hours.
After the reaction is finished, stirring, cooling to 70 ℃, adding N, N-dimethylethanolamine with the same molar weight as G2 and about 0.38G for neutralization for 10min, adjusting the pH value of the system to about 6.5, and then adding 152.07G of deionized water under the stirring action of a high-shear dispersion machine with the rotation speed of 1000-1500r/min until the mass concentration of the system resin is about 40 percent to obtain the water-based emulsion with blue light, namely the water-based acrylate resin dispersion hybridized by the double POSS polyether DPPE-4, which is marked as POSSPA-4, and the hydroxyl content is about 2.18 percent.
Water-based acrylate resin dispersion application: taking the double POSS polyether hybridized water-based acrylate resin dispersoid prepared in the examples 1-4, sequentially adding 0.1-0.3% of defoamer ST2438, 0.2% of BYK-346 leveling agent, 0.3% of Tego 902W defoamer and 0.35% of Tego 752W wetting dispersant according to the mass part of the resin, stirring and uniformly mixing, adding isocyanate curing agent HW3280(BASF) according to the mol ratio of-OH contained in the POSSPA to-NCO contained in the curing agent of 1:1.2-1.5, stirring and mixing uniformly to prepare working solution for spraying, then a rock field spray gun (the caliber phi is about 0.8mm) is used for uniformly spraying the working solution on the surface of the tinplate or the glass substrate, the spraying amount is controlled so that the thickness of the coating is controlled to be 50 +/-5 mu m, then leveling and surface drying at room temperature for 2h, then baking at 70 ℃ for 30min and curing at 120 ℃ for 20min in sequence, and carrying out the following performance measurement after balancing at room temperature for 24 h: measuring the light transmittance (T%) of the coating film by using a Cary 5000 type ultraviolet-visible spectrophotometer, wherein the wavelength range is 200-800 nm, and the reference is blank glass; impact resistance: measured with a QCJ paint film impactor with reference to GB/T1732 + 1993, the gloss: measuring with KGZ-60 type glossometer with reference to GB/T1728-79; hardness: testing with a pencil hardness meter according to GB/T6739-; adhesion force: the test is carried out by a cross-cut test method according to GB/T9286-1998; in addition, PA resins prepared in the same manner without double polyether POSS hybrid modification are used as references in the present invention, and the results are shown in Table 2, taking the reference of example 1 as an example.
TABLE 2 measurement results of dual POSS polyether hybrid PA resin coating film and reference properties
As can be seen from Table 2, the hybrid modification of the PA resin by the bis-POSS polyether has the effect of improving the hardness and the impact resistance of the resin under the condition of not influencing the light transmittance and the glossiness of the resin.
Claims (10)
1. The preparation method of the double POSS polyether hybrid water-based acrylic resin dispersion is characterized by comprising the following steps:
1) carrying out free radical polymerization on the mixed material B1 to generate a polymer surfactant with self-emulsifying function;
2) adding the mixture B2 into the system, and continuing to carry out free radical polymerization to obtain the double POSS polyether hybrid water-based acrylic resin;
3) adding organic base for neutralization, and adjusting the pH value of the system to 6.0-7.5;
4) adding deionized water under the dispersion and stirring of a high-shear machine, and filtering to obtain a water-based emulsion with blue fluorescence, namely a double POSS polyether physically hybridized water-based acrylate resin dispersion;
the mixture B1 is a mixture comprising the following components:
acrylic ester monomer
Non-ester alkenyl monomers
Hydrophilic functional monomer G1
Water-soluble functional monomer G2
Free radical initiator C1
Molecular weight regulator CTA 1;
the mixture B2 is a mixture comprising the following components:
acrylic ester monomer
Non-ester alkenyl monomers
Hydrophilic functional monomer G1
Free radical initiator C2
Molecular weight regulator CTA2
bis-POSS polyethers;
the acrylate monomer is one or more of acrylic ester or methyl acrylic ester containing alkyl with 1-8 carbon atoms;
the structural formula of the double POSS polyether is as follows:
in the formula, R is one or more of isobutyl, isooctyl, octyl and phenyl, and a and b are nonnegative integers;
the hydrophilic functional monomer G1 is an acrylic acid derivative monomer containing hydroxyl;
the water-soluble functional monomer G2 is a carboxylic acid monomer containing alkenyl, the structure of which is shown in formula (2-1) or formula (2-2):
CH2=CHCH2O(C2H4O) a1 (C3H6O) b1 COCH2CH2COOH（2-1）
CH2=CHCH2O(C2H4O) a2 (C3H6O) b2 COCH=CHCOOH（2-2）
in the formula a1、a2、b1、b2Is a non-negative integer;
according to the mass, the total amount of the acrylate monomers in the composition is 36.5-88 parts; the total amount of non-ester alkenyl monomers in the composition is 0-44 parts; the total amount of the hydrophilic functional monomer G1 in the composition is 12-27 parts; the total amount of the water-soluble functional monomer G2 in the composition is 3-6 parts; 2-3.5 parts of total amount of free radical initiators C1 and C2 in the composition; the total amount of molecular weight regulator CTA1+ CTA2 in the composition is 1-3.0 parts; 5-25 parts of bis POSS polyether in the composition;
the mass ratio of the free radical initiator C1 to the free radical initiator C2 is (10-35): (65-90);
the mass ratio of the molecular weight regulator CTA1 to the molecular weight regulator CTA2 is (10-30): (70-90);
the types and the mass ratios of the acrylate monomer, the non-ester alkenyl monomer and the hydrophilic functional monomer G1 in the mixture B1 are all the same as those of the mixture B2; the mass ratio of the acrylate monomer in the mixture B1 to the acrylate monomer in the mixture B2 is (10-30): (70-90).
2. The method of claim 1, wherein the non-ester monomer is one of styrene and acrylonitrile; the hydrophilic functional monomer G1 is one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and N-hydroxymethyl acrylamide.
3. Method according to claim 1 or 2, characterized in that a1、a2、b1、b2Has a value in the range of 0 to 30, and a1+b1、a2+b2The value range of (1) to (30); a. the value range of b is 3-25.
4. The method of claim 1, wherein the step 1) comprises: heating the solvent to 80-130 ℃, slowly dripping the mixture B1, and keeping the system at 80-130 ℃ for full reaction; the solvent is one or more of alcohol, alcohol ether or ester solvents.
5. The method of claim 1, wherein the step 1) comprises: heating the solvent to 80-130 ℃, slowly dripping the mixture B1, and keeping the system at 80-130 ℃ for full reaction; the solvent is alcohol ether ester.
6. The method of claim 1, wherein the step 2) comprises: maintaining the system at 80-130 deg.C, slowly adding mixture B2 dropwise, and maintaining the system at 80-130 deg.C for full reaction.
7. The method of claim 1, wherein the organic base is one or more of N, N-dimethylaminoethanol, ethanolamine, and triethylamine.
8. The process of claim 1, wherein the organic base is diethanolamine.
9. A bis POSS polyether hybrid water-based acrylic resin dispersion prepared by the method of any of claims 1-8.
10. The composition for preparing the double polyether POSS hybrid modified PA resin coating film is characterized by comprising a material A and a material B; the material A comprises 100 parts by mass of the double POSS polyether hybrid water-based acrylic resin dispersoid of claim 9, 0.1-0.3 part by mass of a defoaming agent, 0.2 part by mass of a leveling agent, 0.3 part by mass of a defoaming agent and 0.35 part by mass of a wetting dispersant; the effective component of the material B is isocyanate; the molar ratio of-OH contained in the double POSS polyether hybrid water-based acrylic resin in the material A to-NCO contained in the material B is 1: (1.2-1.5).
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