CN114057935A - Acrylic ester polymer, preparation method and application thereof, acrylic ester polymer coating and application thereof - Google Patents
Acrylic ester polymer, preparation method and application thereof, acrylic ester polymer coating and application thereof Download PDFInfo
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Abstract
The invention provides an acrylic polymer, a preparation method and application thereof, an acrylic polymer coating and application thereof, and relates to the technical field of polymers. The acrylate polymer provided by the invention has a structure shown in a formula I. The acrylic ester polymer provided by the invention has a remarkable hydrophobic property, and can effectively prevent infiltration and permeation of water; meanwhile, the silane molecules in the acrylate polymer are large, so that the polymer has large gaps, free gas micromolecules can pass through the polymer, and the polymer has good air permeability; the acrylate polymer has a local cross-linking structure, so that the flexibility requirement in a service temperature region can be obtained while the strength of the material is remarkably improved, and the defect of hot sticking and cold brittleness of the traditional polyacrylate polymer is overcome; the polyacrylate polymer provided by the invention has strong adhesive force; has good application prospect in the fields of skin care, wound protection, cultural relic restoration, fabric treatment and the like.
Description
Technical Field
The invention relates to the technical field of polymers, and particularly relates to an acrylic ester polymer, a preparation method and application thereof, an acrylic ester polymer coating and application thereof.
Background
The synthetic high molecular polymer is a material which can easily obtain specific performance characteristics through the design of a high molecular structure. Compared with natural polymers, the synthetic high molecular polymer has outstanding advantages in the aspects of mechanical property, processability, structure control, performance regulation and control and the like. However, synthetic polymer materials generally have problems such as low air permeability and poor strength, and thus cannot be widely used in fields requiring air permeability.
The air permeability and strength of the synthetic high molecular polymer can be improved by modifying the synthetic high molecular polymer with modified cellulose, an inorganic material, or the like to form a porous material. For example, chinese patent CN104212208B discloses a silicon-containing acrylate polymer composite porous respiratory coating, which is prepared from acrylate monomers, thermoplastic acrylate polymer, emulsifier, oxidation-reduction initiator and surface-treated porous silicon-containing inorganic filler, and the silicon-containing acrylate polymer porous material formed by curing the coating has high strength, toughness, water permeability and air permeability. However, the above silicon-containing acrylate polymer porous material has poor hydrophobicity.
Disclosure of Invention
In view of the above, the present invention aims to provide an acrylate polymer, a preparation method and applications thereof, an acrylate polymer coating and applications thereof, wherein the acrylate polymer provided by the present invention has excellent hydrophobicity, air permeability, strength and toughness.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an acrylic ester polymer, which has a structure shown in a formula I:
in the formula I, R1、R2、R3、R4And R5Independently comprise C1～C12Alkyl and C1～C12One or more alkyl derivatives; n is 1 to 20; a is 100 to 1000; b is 1 to 20.
The invention provides a preparation method of the acrylate polymer in the technical scheme, which comprises the following steps:
mixing a first part of mixed monomers and a first initiator for a prepolymerization reaction to obtain a prepolymer, wherein the first part of mixed monomers comprise a first silane monomer, a first acrylate monomer and a first cross-linking agent;
mixing the prepolymer, a second part of mixed monomer and a second initiator for polymerization reaction to obtain an acrylate polymer; the second part of mixed monomers comprise a second silane monomer, a second acrylic acid monomer and a second cross-linking agent;
the first silane monomer and the second silane monomer independently comprise one or more of monovinyl-terminated polydimethylsiloxane, vinylmethyldi (dimethylpolysiloxane-yl) silane, methacryloxypropyltri (trimethylsiloxy) silane, 1-methoxy-1- (trimethylsiloxy) -2-methyl-1-propene, vinyloxytrimethylsilane, vinylmethylsiloxane-dimethylsiloxane copolymer, alpha-monovinyl-omega-monohydroxy-terminated polydimethylsiloxane, and alpha-monovinyl-monophenyl-omega-monohydroxy-terminated polydimethylsiloxane.
The first acrylate monomer and the second acrylate monomer independently comprise methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, isobornyl methacrylate, lauryl methacrylate, or lauryl acrylate;
the first crosslinking agent and the second crosslinking agent are independently a monomer having a radically reactive C ═ C double bond or a polymer having a radically reactive C ═ C double bond.
Preferably, the first crosslinking agent and the second crosslinking agent independently comprise one or more of a polyurethane crosslinking agent, a methyl silicone crosslinking agent, an alkenyl benzene crosslinking agent, a diacrylamide crosslinking agent and a polyacrylate crosslinking agent.
Preferably, the mass ratio of the first silane monomer to the first acrylate monomer to the first crosslinking agent is 10-80: 20-70: 0.01 to 1.0;
the mass of the first silane monomer is 5-20% of the total mass of the first silane monomer and the second silane monomer;
the mass of the first acrylate monomer is 5-20% of the total mass of the first acrylate monomer and the second acrylate monomer;
the mass of the first cross-linking agent is 5-20% of the total mass of the first cross-linking agent and the second cross-linking agent.
Preferably, the total mass of the initiator is 0.5-1.2% of the total mass of the silane monomer and the acrylate monomer;
the mass of the first initiator is 10-40% of the total mass of the first initiator and the second initiator.
Preferably, the temperature of the prepolymerization reaction is 70-90 ℃, and the time is 30-60 min.
Preferably, the mass ratio of the second silane monomer, the second acrylate monomer and the second cross-linking agent is 10-80: 20-70: 0.01 to 1.0.
Preferably, the temperature of the polymerization reaction is 80-85 ℃, and the time is 2-8 h.
The invention provides an acrylic ester polymer coating, which comprises the acrylic ester polymer in the technical scheme or the acrylic ester polymer obtained by the preparation method in the technical scheme, a solvent and an additive;
the additive comprises one or more of bactericide, anti-inflammatory drug, mildew preventive, preservative, algaecide and antioxidant.
The invention also provides the application of the acrylic polymer in the technical scheme, the acrylic polymer obtained by the preparation method in the technical scheme or the acrylic polymer coating in the technical scheme in cultural relic protection, cultural relic restoration, fabric treatment, non-treatment purpose wound protection or non-treatment purpose skin care.
The invention provides an acrylic ester polymer with a structure shown in a formula I, wherein R in the formula I1、R2、R3、R4And R5Independently comprise C1～C12Alkyl and C1～C12One or more alkyl derivatives; n is 1 to 20; a is 100 to 1000; b is 1 to 20. The silane monomer is introduced into the acrylate polymer, so that the infiltration and permeation of water can be effectively prevented, and the acrylate polymer has remarkable hydrophobic property; meanwhile, the silane molecules in the acrylate polymer are large, so that the polymer has large gaps, free gas micromolecules can pass through the polymer, and the polymer has good air permeability; the acrylate polymer has a partially crosslinked structure and canThe strength of the material is remarkably improved, the flexibility requirement in a service temperature region (30-40 ℃) is obtained, and the defect that the traditional polyacrylate polymer is hot-bonded and cold-brittle is overcome. Moreover, the acrylic polymer has good solubility in a solvent and excellent film forming property, so that the acrylic polymer has strong adhesive force on the surfaces of skin, glass, PET, metal, cement, fabrics, stone and the like, the outer surface of the acrylic polymer is soft and non-sticky, and the defects of hot adhesion and cold brittleness of the acrylic polymer are effectively overcome. The acrylic ester polymer provided by the invention has the characteristics of high strength, strong adhesive force, excellent hydrophobicity and air permeability and the like, so that the acrylic ester polymer has good application prospects in the fields of skin care, wound protection, cultural relic repair, fabric treatment and the like.
Compared with the prior art, the acrylic polymer with hydrophobic property is synthesized by selecting specific silane monomers, acrylate monomers and cross-linking agents and utilizing the characteristic of large structural space volume of silane, and the monomer or polymer cross-linking agent with C ═ C double bond and free radical reaction activity forms a controllable local cross-linking system in the polymerization reaction process, so that the problems that the molecular weight is small and the polymer material with application value is difficult to obtain due to large steric hindrance in the polymerization reaction of the silane monomers are solved, the high-strength hydrophobic breathable polymer material with excellent performance is obtained, and the defect that the traditional polyacrylate polymer is hot-sticky and cold-brittle is overcome; can meet the performance requirements at different service temperatures (30-40 ℃). The obtained polymer has wide solubility in polar and non-polar solvents and excellent film forming property. The acrylic ester polymer coating film has remarkable hydrophobic property and can effectively prevent moisture from infiltrating and permeating; meanwhile, the silane molecules in the acrylate polymer are large, so that the polymer has large gaps, free gas micromolecules can pass through the polymer, the polymer has good air permeability, and the transmission of the gas molecules is not influenced. The acrylic ester polymer provided by the invention has the characteristics of high strength, strong adhesive force, excellent hydrophobicity and air permeability and the like, so that the acrylic ester polymer has good application prospects in the fields of skin care, wound protection, cultural relic repair, fabric treatment and the like.
The preparation method provided by the invention is simple to operate, low in production cost and suitable for industrial production.
The invention also provides an acrylic ester polymer coating, which comprises the acrylic ester polymer in the technical scheme or the acrylic ester polymer obtained by the preparation method in the technical scheme, a solvent and an additive; the additive comprises one or more of bactericide, anti-inflammatory drug, mildew preventive, preservative, algaecide and antioxidant. In the acrylic ester polymer coating provided by the invention, the silane molecules in the acrylic ester polymer are relatively large, so that the polymer has relatively large gaps, free gas micromolecules can pass through the polymer, the acrylic ester polymer coating has good air permeability, and the transmission of the gas molecules is not influenced. The acrylic ester polymer provided by the invention has the characteristics of high strength, strong adhesive force, excellent hydrophobicity and air permeability and the like, so that the acrylic ester polymer has good application prospects in the fields of skin care, wound protection, cultural relic repair, fabric treatment and the like
Drawings
FIG. 1 is a graph showing the results of a contact angle test of the acrylate-based polymer prepared in example 1;
FIG. 2 is a graph of the dynamic thermo-mechanical property results for the acrylate polymer prepared in example 1;
FIG. 3 is a graph showing the results of a contact angle test of the acrylate-based polymer prepared in example 2;
FIG. 4 is a graph showing the results of thermal performance tests on the acrylate polymer prepared in example 2;
FIG. 5 is a graph of the dynamic thermo-mechanical property results for the acrylate polymer prepared in example 2;
FIG. 6 is a graph showing the results of the water resistance test of the anti-algae protectant prepared in example 3;
FIG. 7 is a graph of the results of the anti-algal test for the anti-algal protectant prepared in example 3;
FIG. 8 is a graph showing the results of the water repellency test of the skin care/wound protection agent prepared in example 4, wherein a is a human body and b is a rabbit;
fig. 9 is a graph of the hemostatic performance of the skin care/wound protectant prepared in example 4.
Detailed Description
The invention provides an acrylic ester polymer, which has a structure shown in a formula I:
in the invention, in the formula I, R1、R2、R3、R4And R5Independently comprise C1～C12Alkyl and C1～C12One or more alkyl derivatives; said C is1～C12Alkyl and C1～C12C in alkyl derivatives1～C12The alkyl group independently includes a straight-chain alkyl group or a branched-chain alkyl group, and specifically preferably includes one or more of a methyl group, an ethyl group, a straight-chain propyl group, a branched-chain propyl group, a straight-chain butyl group, a branched-chain butyl group, a straight-chain pentyl group, a branched-chain pentyl group, a straight-chain hexyl group, a branched-chain hexyl group, a straight-chain heptyl group, a branched-chain heptyl group, a straight-chain octyl group, a branched-chain nonyl group, a straight-chain decyl group, a branched-chain decyl group, a straight-chain undecyl group, a branched-chain undecyl group, a straight-chain dodecyl group and a branched-chain dodecyl group. In the invention, n in the formula I is preferably 1-20, preferably 5-15, and more preferably 5-10. In the invention, a in the formula I is 100-1000, preferably 200-700, and more preferably 300-500. In the invention, b in the formula I is 1-20, preferably 5-15, and more preferably 5-10. In the invention, the number average molecular weight of the acrylate polymer is preferably 50000-150000, more preferably 70000-120000; the weight average molecular weight of the acrylate polymer is preferably 80000-280000, more preferably 100000-250000; the molecular weight distribution index of the acrylate polymer is preferably 1.2-2.8, and more preferably 1.4-2.6. The acrylic ester polymer provided by the invention has ideal molecular weight, good polymer film-forming property, outstanding mechanical property and flexible and non-sticky characteristics.
The invention provides a preparation method of the acrylate polymer in the technical scheme, which comprises the following steps:
mixing a first part of mixed monomers and a first initiator for a prepolymerization reaction to obtain a prepolymer, wherein the first part of mixed monomers comprise a first silane monomer, a first acrylate monomer and a first cross-linking agent;
mixing the prepolymer, a second part of mixed monomer and a second initiator for polymerization reaction to obtain an acrylate polymer; the second part of mixed monomers comprise a second silane monomer, a second acrylic acid monomer and a second cross-linking agent;
the first and second silane monomers independently comprise MonoVinyl-Terminated PolyDimethylsiloxane, vinylmethyldi (dimethylpolysiloxy) silane, methacryloxypropyltris (trimethylsiloxy) silane, 1-methoxy-1- (trimethylsiloxy) -2-methyl-1-propene, vinyloxytrimethylsilane, vinylmethylsiloxane-dimethylsiloxane copolymer, α -MonoVinyl- Ω -monohydroxy-Terminated PolyDimethylsiloxane (Siloxanes and Silicones, di-Me, hydrogen-and vinyl group-Terminated, CAS 104780-63-4), and α -MonoVinyl-MonoPhenyl- Ω -monohydroxy-Terminated PolyDimethylsiloxane (α -MonoVinyl-MonoPhonyl- Ω -Mono hydrogenated polymerized dimethylsiloxane), one or more of CAS 1422279-25-1);
the first acrylate monomer and the second acrylate monomer independently comprise methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, isobornyl methacrylate, lauryl methacrylate, or lauryl acrylate;
the first crosslinking agent and the second crosslinking agent are independently a monomer having a radically reactive C ═ C double bond or a polymer having a radically reactive C ═ C double bond.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, a first part of mixed monomers and a first initiator are mixed for a prepolymerization reaction to obtain a prepolymer, wherein the first part of mixed monomers comprise a first silane monomer, a first acrylate monomer and a first cross-linking agent.
In the present invention, the first silane monomer includes one or more of MonoVinyl-Terminated PolyDimethylsiloxane, vinylmethyldi (dimethylpolysiloxane-yl) silane, methacryloxypropyltris (trimethylsiloxy) silane, 1-methoxy-1- (trimethylsiloxy) -2-methyl-1-propene, vinyloxytrimethylsilane, vinylmethylsiloxane-dimethylsiloxane copolymer, Siloxanes and Silicones, di-Me, hydrogen-and vinyl group-Terminated (CAS: 104780-63-4), and α -MonoVinyl-MonoPhonyl- Ω -MonoHydrodride Terminated polydimethylsiloxanes (CAS: 1422279-25-1). In the present invention, the first silane monomer is preferably subjected to a purification treatment to remove the polymerization inhibitor in the monomer before use, and the purification treatment preferably includes an alkali washing purification, a silica gel column purification or an activated carbon adsorption purification. In the invention, the alkali washing purification is preferably to place the first silane monomer in alkali liquor for mixing, then to stand for phase separation, to dry the obtained organic phase with a drying agent and then to filter; the alkali in the alkali liquor preferably comprises sodium hydroxide solution; the concentration of the alkali liquor is preferably 0.5-3.5 mol/L, and more preferably 1-2.5 mol/L; the mixing is preferably shaking mixing; the drying agent preferably comprises anhydrous calcium chloride and anhydrous sodium sulfate, and the mass ratio of the first silane monomer to the drying agent is preferably 1: 0.2 to 1.5, more preferably 1: 0.5-1.0; the drying time is preferably 4-14 h, and more preferably 6 h. In the present invention, the conditions for the silica gel column purification and the activated carbon adsorption purification are not particularly limited, and the prepolymer can be obtained by separation.
In the present invention, the first acrylate monomer includes methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, isobornyl methacrylate, lauryl methacrylate, or lauryl acrylate. In the invention, the first acrylate monomer is preferably subjected to purification treatment before use; the method of the purification treatment is preferably the same as the method of the purification treatment of the first silane monomer, and is not described herein again; the purpose of the purification treatment is to remove polymerization inhibitors.
In the invention, the first cross-linking agent is a monomer with C ═ C double bond with free radical reaction activity or a polymer with C ═ C double bond with free radical reaction activity, and preferably comprises one or more of polyurethane cross-linking agent, methyl silicone oxygen cross-linking agent, alkenyl benzene cross-linking agent, diacrylamide cross-linking agent and polyacrylate cross-linking agent; the polyurethane crosslinking agent preferably comprises polyurethane with end-capped C ═ C double bonds; the methyl silicone cross-linking agent preferably comprises divinyl terminated polydimethyl siloxane and/or diallyl dimethyl silane; the alkenylbenzene-based crosslinking agent preferably includes divinylbenzene; the diacrylamide-based crosslinking agent preferably comprises N, N-methylenebisacrylamide; the polyacrylate crosslinking agent comprises one or more of diacrylate crosslinking agent, triacrylate crosslinking agent and tetraacrylate crosslinking agent, and the diacrylate crosslinking agent preferably comprises 1, 6-hexanediol diacrylate; the triacrylate crosslinking agent preferably comprises one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate; the tetraacrylate crosslinker preferably comprises pentaerythritol tetraacrylate and/or ethoxylated urethane tetraacrylate. In the present invention, the first crosslinking agent is preferably subjected to a cleaning treatment before use; the method of the purification treatment is preferably the same as the method of the purification treatment of the first silane monomer, and is not described herein again; the purpose of the purification treatment is to remove polymerization inhibitors.
In the invention, in the first part of mixed monomers, the mass ratio of the first silane monomer, the first acrylate monomer and the first cross-linking agent is preferably 10-80: 20-70: 0.01 to 1.0, more preferably 20 to 60: 30-60: 0.1 to 0.8, preferably 30 to 50: 40-50: 0.3 to 0.5. In the invention, the mass of the first part of mixed monomers is 5-25%, preferably 10-20%, and more preferably 15-20% of the total mass of the first part of mixed monomers and the second part of mixed monomers. In the present invention, the mass of the first silane monomer is preferably 5 to 20%, and more preferably 10 to 15% of the total mass of the first silane monomer and the second silane monomer. In the present invention, the mass of the first acrylate monomer is preferably 5 to 20%, and more preferably 10 to 15% of the total mass of the first acrylate monomer and the second acrylate monomer. In the present invention, the mass of the first crosslinking agent is preferably 5 to 20%, more preferably 10 to 15% of the total mass of the first crosslinking agent and the second crosslinking agent.
In the present invention, the first initiator preferably comprises Azobisisobutyronitrile (AIBN) and/or Azobisisoheptonitrile (ABVN). In the invention, the total mass of the first initiator is 0.5-1.2% of the total mass of the silane monomer and the acrylate monomer, more preferably 0.6-1%, and even more preferably 0.8-0.9%. In the present invention, the first initiator preferably accounts for 10 to 40%, preferably 20 to 30%, and more preferably 25% of the total mass of the first initiator and the second initiator. In the present invention, the first initiator is preferably subjected to a purification treatment before use, the purification treatment is preferably performed by recrystallization, the organic solvent for recrystallization preferably includes an alcohol solvent, and the alcohol solvent is preferably ethanol; the number of recrystallization is preferably 2 to 3.
In the present invention, the solvent for the prepolymerization preferably comprises one or more of ethyl acetate, butyl acetate, acetone and carbon tetrachloride. In the present invention, the mass ratio of the mixed monomer to the solvent for preliminary polymerization is preferably 1: 0.3 to 1.5, more preferably 1: 0.5 to 1.
The mixing mode is not specific, and the raw materials can be uniformly mixed, such as stirring and mixing; the mixing temperature is preferably 70-90 ℃, more preferably 75-85 ℃, and most preferably 80 ℃. In the present invention, the mixing order is preferably to add the first part of the mixed monomers after premixing the first initiator solution and the solvent; the time for premixing is preferably 5-30 min, and more preferably 10-20 min. In the present invention, the initiator is thermally decomposed during the mixing process to remove impurities in the solvent having an effect of inhibiting polymerization of free radicals.
In the invention, the temperature of the prepolymerization reaction is preferably 70-90 ℃, more preferably 75-85 ℃, and most preferably 80 ℃, and the time of the prepolymerization reaction is preferably 30-60 min, more preferably 35-55 min, and further preferably 40-50 min.
After obtaining the prepolymer, mixing the prepolymer, a second part of mixed monomer and a second initiator for polymerization reaction to obtain an acrylate polymer; the second portion of mixed monomers includes a second silane monomer, a second acrylic monomer, and a second crosslinker.
In the present invention, the second silane monomer, the second acrylic monomer, the second crosslinking agent, and the second initiator are preferably the same as the first silane monomer, the first acrylic monomer, the first crosslinking agent, and the first initiator, respectively, and are not described in detail herein. In the present invention, the second silane monomer is preferably the same as the first silane monomer; the second acrylic monomer is preferably the same as the first acrylic monomer; the second crosslinking agent is preferably the same as the first crosslinking agent.
The mixing mode is not specific, and the raw materials can be uniformly mixed, such as stirring and mixing; the mixing temperature is preferably 80-85 ℃, more preferably 81-84 ℃, and further preferably 82-83 ℃. In the invention, the polymerization reaction temperature is preferably 80-85 ℃, and the time is preferably 2-8 h.
In the embodiment of the present invention, the prepolymer, the second part of mixed monomer, and the second initiator are mixed to perform a polymerization reaction, preferably, the second part of mixed monomer and a part of the second initiator are mixed and then added to the prepolymer first drop to perform a first radical polymerization reaction, and the remaining second initiator is dissolved in an organic solvent to obtain a remaining initiator solution; and secondly, dropwise adding the residual initiator solution into the system of the first free radical polymerization reaction to carry out second free radical polymerization reaction. In the invention, the part of the second initiator preferably accounts for 10-60% of the mass of the second initiator, and more preferably accounts for 20-50%. In the invention, the first dripping time is preferably 1.5-2.5 h, and more preferably 2 h. In the invention, the temperature of the first free radical polymerization reaction is preferably 80-85 ℃, more preferably 81-84 ℃, and further preferably 82-83 ℃; the time of the first free radical polymerization reaction is preferably 1-2 h, and more preferably 1.5-2 h; … … during the first free radical polymerization reaction. In the present invention, the organic solvent preferably includes one or more of ethyl acetate, butyl acetate, acetone and carbon tetrachloride; the mass of the organic solvent is preferably 5-30% of the total mass of the silane monomer and the acrylate monomer, and more preferably 10-20%. In the invention, the second dripping is preferably carried out for 1-2 times; the second dripping speed is not specially limited, and the second dripping speed is uniform dripping speed. In the invention, the temperature of the second free radical polymerization reaction is preferably 80-85 ℃, more preferably 81-84 ℃, and further preferably 82-83 ℃; the time of the second free radical polymerization reaction is preferably 1-6 h, and more preferably 2-5 h. In the present invention, the polymerization reaction is preferably carried out under air or a protective atmosphere, the protective atmosphere preferably comprising nitrogen or an inert gas, the inert gas preferably comprising argon or helium; when the polymerization reaction is carried out under a protective atmosphere, the problem of oxygen inhibition in the polymerization reaction process can be reduced, and the molecular weight of the polymer is further improved.
After the polymerization reaction, the invention preferably further comprises post-treating the system of the polymerization reaction to obtain the acrylate polymer. In the present invention, the post-treatment comprises cooling, precipitation and solid-liquid separation in this order, and then the resulting solid product is dried. The cooling method is not particularly limited, and the cooling is performed until the temperature is 30-60 ℃, and more preferably 40-50 ℃. In the present invention, the precipitant for precipitation preferably includes an alcohol solvent, an ether solvent or water; the alcohol solvent preferably comprises methanol and/or ethanol; the ether solvent preferably includes diethyl ether; the mass ratio of the precipitating agent to the total mass of the silane monomer and the acrylate monomer is 1: 0.5 to 1.5, more preferably 1: 1 to 1.2; the precipitation mode is preferably cooling under the stirring condition; the stirring speed and time are not specially limited, and the precipitates are not increased; the cooling method is not particularly limited, and a cooling method known to those skilled in the art may be adopted, specifically, natural cooling is adopted. The solid-liquid separation mode is not particularly limited, and a solid-liquid separation mode known to those skilled in the art can be adopted, specifically centrifugal separation; the number of times of precipitation is preferably 1-2 times. In the invention, the drying temperature is preferably 40-110 ℃, more preferably 50-100 ℃, and further preferably 60-80 ℃; the drying time is preferably 6-48 h, more preferably 10-40 h, and further preferably 20-30 h; the drying mode is preferably vacuum drying.
The invention provides an acrylic ester polymer coating, which comprises the acrylic ester polymer in the technical scheme or the acrylic ester polymer obtained by the preparation method in the technical scheme, a solvent and an additive.
In the invention, the additive comprises one or more of a bactericide, an anti-inflammatory drug, a mildew preventive, a preservative, an algaecide and an antioxidant; the mass of the additive is preferably 0.01-10%, more preferably 0.1-5% of the mass of the acrylate polymer. In the invention, the bactericide preferably comprises one or more of benzethonium chloride, Gemini quaternary ammonium salt and lavender essential oil; the addition amount of the bactericide is preferably 0.02 to 5%, more preferably 0.1 to 3%, and further preferably 1 to 2%. In the invention, the anti-inflammatory drugs preferably comprise one or more of penicillins, aminoglycosides and cephalosporins; the addition amount of the anti-inflammatory drug is preferably 0.01 to 0.5%, more preferably 0.1 to 0.4%, and even more preferably 0.2 to 0.3%. In the present invention, the mildewcide preferably includes a quaternary ammonium salt derivative and/or cason; the addition amount of the mildew inhibitor is preferably 0.1-2%, more preferably 0.5-1.5%, and even more preferably 1-1.2%. In the present invention, the preservative preferably comprises benzethonium chloride; the addition amount of the preservative is preferably 0.02 to 0.2%, more preferably 0.05 to 0.15%, and still more preferably 0.1 to 0.12%. In the present invention, the algae-preventing component preferably includes capsaicin and/or Preventol A9-D; the addition amount of the algae-preventing component is preferably 0.02 to 5%, more preferably 0.1 to 3%, and further preferably 1 to 2%. In the invention, the antioxidant is preferably an ultraviolet resistant oxidant, and the ultraviolet resistant oxidant preferably comprises one or more of p-hydroxy tert-butyl anisole (BHA), Irganox 1010, Irganox1076 and nano titanium dioxide; the addition amount of the antioxidant is preferably 0.5 to 10%, more preferably 1 to 8%, and further preferably 3 to 5%.
In the invention, the solvent preferably comprises one or more of an alcohol solvent, an ester solvent, an alkane solvent, an ether solvent and a siloxane solvent, and the alcohol solvent preferably comprises ethanol and/or isopropanol; the ester solvent preferably includes ethyl acetate and/or butyl acetate; the alkane solvent preferably comprises one or more of pentane, hexane, isooctane and cyclohexane; the ether solvent preferably comprises one or more of ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether and propylene glycol monobutyl ether; the siloxane-based solvent preferably comprises hexamethyldisiloxane; the concentration of the acrylic polymer in the acrylic polymer coating is preferably 5 to 60 wt%, more preferably 6 to 50 wt%, and still more preferably 20 to 30 wt%.
The invention provides an application of the acrylate polymer in the technical scheme, the acrylate polymer obtained by the preparation method in the technical scheme or the acrylate polymer coating in the technical scheme in cultural relic protection, cultural relic restoration, fabric treatment, non-treatment purpose wound protection or non-treatment purpose skin care.
In the invention, the cultural relics in the cultural relic protection and the cultural relic restoration independently comprise stone cultural relics and/or soil cultural relics.
In the invention, the application mode of the acrylic polymer coating is preferably spraying, brushing, rolling or dipping; the present invention is not particularly limited with respect to the specific operation of spraying, brushing, rolling or dipping, and spraying, brushing, rolling or dipping operations well known to those skilled in the art may be used.
Compared with the prior art, the acrylic polymer with hydrophobic property is artificially synthesized by selecting specific silane monomers, acrylate monomers and cross-linking agents and utilizing the characteristic of large structural space volume of silane, and the monomer or polymer cross-linking agent with C ═ C double bond and free radical reaction activity forms a controllable local cross-linking system in the polymerization reaction process, so that the problems that the molecular weight is small and the polymer material with application value is difficult to obtain due to large steric hindrance in the polymerization reaction of the silane monomers are solved, the high-strength hydrophobic breathable polymer material with excellent performance is obtained, and the defect that the traditional polyacrylate polymer is hot-sticky and cold-brittle is overcome; the performance requirements at different service temperatures can be met by adjusting the polymer composition and structure. The obtained polymer has wide solubility in polar and non-polar solvents and excellent film forming property. The acrylic ester polymer coating film has remarkable hydrophobic property and can effectively prevent moisture from infiltrating and permeating; meanwhile, the silane molecules in the acrylate polymer are large, so that the polymer has large gaps, free gas micromolecules can pass through the polymer, the polymer has good air permeability, and the transmission of the gas molecules is not influenced. The acrylate polymer has the characteristics of high strength, strong adhesive force, excellent hydrophobicity and air permeability and the like, so that the acrylate polymer has good application prospects in the fields of skin care, wound protection, cultural relic repair, fabric treatment and the like.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Respectively placing methyl methacrylate, 2-ethylhexyl acrylate, vinyloxytrimethylsilane and vinylmethylsiloxane-dimethylsiloxane in a sodium hydroxide solution with the concentration of 2mol/L, fully mixing at room temperature to remove a polymerization inhibitor, discarding a water phase, adding anhydrous calcium chloride into the organic phase containing the monomers, drying for 6 hours, and filtering for later use; and recrystallizing AIBN by using absolute ethyl alcohol for 2-3 times, naturally airing at room temperature for 24 hours, and storing at low temperature for later use.
Uniformly mixing 30g of methyl methacrylate, 15g of 2-ethylhexyl acrylate, 40g of vinyloxytrimethylsilane, 15g of vinyl methyl siloxane-dimethyl siloxane and 0.5g of 1, 6-hexanediol diacrylate to obtain a mixed monomer;
adding 0.275g of AIBN and 100g of ethyl acetate into a three-neck flask, mixing for 15min at the temperature of 80 ℃ under stirring, adding 15g of mixed monomer, and performing prepolymerization reaction for 30min at the temperature of 80 ℃ to obtain a prepolymer;
mixing 85.5g of mixed monomer and 0.425g of AIBN, dropwise adding the mixture into a three-neck flask at 82 ℃, dropwise adding for 2 hours, preserving heat for 1 hour of first free radical polymerization reaction after dropwise adding is finished, dissolving 0.2g of AIBN in 10g of ethyl acetate, dropwise adding the obtained AIBN solution into the three-neck flask, preserving heat for 3 hours of second free radical polymerization reaction after dropwise adding is finished, cooling the mixture to 50 ℃ in an ice water bath, adding 120g of anhydrous methanol under stirring, continuously cooling the mixture to 50 ℃ until the polymer is completely separated out, discarding supernatant, blade-coating the obtained solid product on a polypropylene film, and drying the polypropylene film at 80 ℃ for 24 hours to obtain the acrylic ester polymer (transparent solid).
Example 2
Respectively placing methyl methacrylate, ethyl acrylate, lauryl methacrylate and methacryloxypropyl tris (trimethylsiloxy) silane in a sodium hydroxide solution with the concentration of 1.2mol/L, fully oscillating, standing for phase separation, removing a water phase to remove a polymerization inhibitor, adding anhydrous calcium chloride in the obtained organic phase, drying for 6 hours, and filtering for later use; and recrystallizing AIBN by using absolute ethyl alcohol for 2-3 times, naturally airing at room temperature for 24 hours, and storing at low temperature for later use.
Uniformly mixing 40g of methyl methacrylate, 10g of ethyl acrylate, 5g of lauryl methacrylate, 30g of methacryloxypropyl tris (trimethylsiloxy) silane and 0.3g of propoxylated trimethylolpropane triacrylate to obtain a mixed monomer;
adding 0.365g of AIBN and 80g of ethyl acetate into a three-neck flask, mixing for 15min at the temperature of 80 ℃ under stirring, adding 20g of mixed monomer, and performing prepolymerization reaction for 30min at the temperature of 80 ℃ to obtain a prepolymer;
mixing 80.3g of mixed monomer and 0.3g of AIBN, dropwise adding the mixture into a three-neck flask at the temperature of 80 ℃, dropwise adding for 2 hours, preserving heat for 1 hour after dropwise adding, dissolving 0.095g of AIBN in 5g of ethyl acetate, dropwise adding the obtained AIBN solution into the three-neck flask, preserving heat for 6 hours after dropwise adding, cooling the mixture to 50 ℃ in an ice water bath, adding 120g of anhydrous methanol under stirring, continuously cooling the mixture until the polymer is completely separated out at room temperature, discarding supernatant, blade-coating the obtained solid product on a polypropylene film, and drying the polypropylene film at the temperature of 80 ℃ for 24 hours to obtain the acrylate polymer (transparent solid).
Test example 1
Performance testing of the acrylic polymers prepared in examples 1-2: the contact angle is tested by using a surface tension meter, the molecular weight is tested by using a gel permeation chromatograph, the thermal performance is tested by using a dynamic thermal analyzer, the dynamic thermal mechanical performance is tested by using a dynamic thermal mechanical analyzer, and the test results are shown in table 1-6.
The molecular weight test results showed that the number average molecular weight Mn of the acrylate polymer prepared in example 1 was 71880, the weight average molecular weight Mw was 118933, and the Mw/Mn was 1.65. Fig. 1 is a graph showing the result of a contact angle test of the acrylate polymer prepared in example 1, and it can be seen from fig. 1 that the acrylate polymer prepared in example 1 has a contact angle of 99.1 ° and is hydrophobic. FIG. 2 is a graph showing the results of the dynamic thermo-mechanical properties of the acrylate polymer prepared in example 1, and it can be seen from FIG. 2 that the strength of the acrylate polymer prepared in example 1 is not less than 20MPa at a temperature of not more than 35 ℃ and can meet the general requirements of the application field of stone/soil cultural relic protection.
The molecular weight measurement result showed that the number average molecular weight Mn of the acrylic polymer prepared in example 2 was 71880, the weight average molecular weight Mw was 118933, and Mw/Mn was 1.41. Fig. 3 is a graph showing the result of the contact angle test of the acrylate polymer prepared in example 2, and it can be seen from fig. 3 that the acrylate polymer prepared in example 2 has a contact angle of 112.0 ° and is significantly hydrophobic. FIG. 4 is a graph showing the results of the thermal property test of the acrylate polymer prepared in example 2, and it can be seen from FIG. 4 that the acrylate polymer prepared in example 2 has stable thermal properties at 10 to 100 ℃. Fig. 5 is a graph showing the dynamic thermo-mechanical property results of the acrylate polymer prepared in example 2, and it can be seen from fig. 5 that the acrylate polymer prepared in example 2 has stable mechanical properties within a human body surface temperature range of 30 to 40 ℃.
Example 3
Stone/soil cultural relic protective agent
The acrylic polymer prepared in example 1 was pulverized to a particle size of less than 1mm to obtain an acrylic polymer powder; dissolving 20g of acrylate polymer powder in 120g of a mixed solvent of ethyl acetate-ethanol (volume ratio is 2: 1), adding 0.15g of Gemini quaternary ammonium salt and 0.05g of capsaicin, and ultrasonically mixing for 60min to obtain the anti-algae protective agent (viscous semitransparent liquid).
Test example 2
The anti-algae protective agent prepared in the embodiment 3 is coated on the surface of the stone to form an anti-algae protective coating, and the visual inspection of the anti-algae protective coating has good film forming property.
The adhesive force of the anti-algae protective coating is tested by a cross-cut method, and the test result is more than or equal to level 1, which shows that the adhesive force of the acrylate polymer prepared by the invention is strong.
The algae-resistant protective coating is respectively placed in air (dry state) and air with the relative humidity of 50 percent and deionized water for soaking for 30 days, and the water resistance test result is shown in figure 6. As can be seen from FIG. 6, the anti-algae protective coating does not have a significant effect on the appearance and color of the stone, and does not have the defects of blushing, peeling, cracking, peeling and the like after being soaked in deionized water for 30 days, which shows that the acrylic ester polymer prepared by the invention has excellent water resistance.
The same amount of the agriophyllum nodosum was inoculated on the surface of the blank glass and the anti-algae protective coating, and cultured in an incubator at 30 ℃ for 24 hours, and the anti-algae test result is shown in 7. As can be seen from FIG. 7, the anti-algae protective coating provided by the present invention has a significant inhibition effect on the attachment and growth of organisms on the surface thereof.
Example 4
Skin care/wound protection agent
The acrylic polymer prepared in example 2 was pulverized to a particle size of less than 1mm to obtain an acrylic polymer powder; 10g of acrylate polymer powder is placed in 90g of mixed solvent of isooctane-ethanol (volume ratio is 100: 1) and stirred at 50 ℃ until being dissolved, 0.05g of lavender essential oil, 0.02g of turpentine and 0.01g of benzylbenzyl ammonium chloride are added and then ultrasonically mixed for 60min, and the skin care/wound protective agent (viscous semitransparent liquid) is obtained.
Test example 3
And (3) testing the waterproof effect: and respectively and uniformly spraying the polymer solution on the surface of dry and clean damaged skin of a human body and the surface of the damaged skin of a rabbit after the hair is removed from the epidermis, and naturally drying to form a compact and continuous film. The results of the water repellency test are shown in FIG. 8, where a is human and b is rabbit. As can be seen from FIG. 8, after the care agent is coated on the skin surface of the human body, the skin surface has obvious hydrophobic effect, and water drops can not be wetted on the skin surface; after the hair of the rabbit epidermis is removed, the rabbit epidermis is coated with a skin care agent, the surface has hydrophobic property, and the wound is difficult to be wetted by water so as to achieve the purpose of skin protection; the polymer prepared by the invention is used for treating skin wounds and has remarkable water pollution resistance.
And (3) testing the hemostatic performance: the skin nursing agent is applied to wounds and surrounding tissues to stop bleeding, and forms a protective coating after being naturally dried. The results of the hemostatic performance test are shown in fig. 9. As can be seen from fig. 9, the skin care/wound protectant prepared in example 4 is used for treating contusion wounds and incised wounds on the body surfaces of animals (rabbits), and shows obvious hemostatic and protective effects.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An acrylic polymer having a structure represented by formula I:
in the formula I, R1、R2、R3、R4And R5Independently comprise C1～C12Alkyl and C1～C12One or more alkyl derivatives; n is 1 to 20; a is 100 to 1000; b is 1 to 20.
2. The method for preparing an acrylic polymer according to claim 1, comprising the steps of:
mixing a first part of mixed monomers and a first initiator for a prepolymerization reaction to obtain a prepolymer, wherein the first part of mixed monomers comprise a first silane monomer, a first acrylate monomer and a first cross-linking agent;
mixing the prepolymer, a second part of mixed monomer and a second initiator for polymerization reaction to obtain an acrylate polymer; the second part of mixed monomers comprise a second silane monomer, a second acrylic acid monomer and a second cross-linking agent;
the first silane monomer and the second silane monomer independently comprise one or more of monovinyl-terminated polydimethylsiloxane, vinylmethyldi (dimethylpolysiloxane-yl) silane, methacryloxypropyltri (trimethylsiloxy) silane, 1-methoxy-1- (trimethylsiloxy) -2-methyl-1-propene, vinyloxytrimethylsilane, vinylmethylsiloxane-dimethylsiloxane copolymer, alpha-monovinyl-omega-monohydroxy-terminated polydimethylsiloxane, and alpha-monovinyl-monophenyl-omega-monohydroxy-terminated polydimethylsiloxane.
The first acrylate monomer and the second acrylate monomer independently comprise methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, isobornyl methacrylate, lauryl methacrylate, or lauryl acrylate;
the first crosslinking agent and the second crosslinking agent are independently a monomer having a radically reactive C ═ C double bond or a polymer having a radically reactive C ═ C double bond.
3. The method according to claim 2, wherein the first crosslinking agent and the second crosslinking agent independently comprise one or more of a polyurethane crosslinking agent, a methyl silicone crosslinking agent, an alkenylbenzene crosslinking agent, a diacrylamide crosslinking agent, and a polyacrylate crosslinking agent.
4. The preparation method according to claim 2 or 3, wherein the mass ratio of the first silane monomer, the first acrylate monomer and the first crosslinking agent is 10-80: 20-70: 0.01 to 1.0;
the mass of the first silane monomer is 5-20% of the total mass of the first silane monomer and the second silane monomer;
the mass of the first acrylate monomer is 5-20% of the total mass of the first acrylate monomer and the second acrylate monomer;
the mass of the first cross-linking agent is 5-20% of the total mass of the first cross-linking agent and the second cross-linking agent.
5. The preparation method according to claim 2, wherein the total mass of the initiator is 0.5-1.2% of the total mass of the silane monomer and the acrylate monomer;
the mass of the first initiator is 10-40% of the total mass of the first initiator and the second initiator.
6. The method according to claim 2, 3 or 5, wherein the temperature of the prepolymerization is 70 to 90 ℃ and the time is 30 to 60 min.
7. The method according to claim 2, 3 or 5, wherein the mass ratio of the second silane monomer, the second acrylate monomer and the second crosslinking agent is 10 to 80: 20-70: 0.01 to 1.0.
8. The method according to claim 2, 3 or 5, wherein the polymerization reaction is carried out at a temperature of 80 to 85 ℃ for 2 to 8 hours.
9. An acrylic polymer coating comprising the acrylic polymer according to claim 1 or the acrylic polymer obtained by the production method according to any one of claims 2 to 8, a solvent and an additive;
the additive comprises one or more of bactericide, anti-inflammatory drug, mildew preventive, preservative, algaecide and antioxidant.
10. Use of the acrylic polymer according to claim 1, the acrylic polymer obtained by the production method according to any one of claims 2 to 8, or the acrylic polymer coating according to claim 9 for cultural relic protection, cultural relic restoration, textile treatment, non-therapeutic wound protection, or non-therapeutic skin care.
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