CN104804111A - Synthetic method and application of Michler's ketone photo-initiator - Google Patents

Abstract

The invention discloses a compound of structural formula (I) and its application as a photoinitiator, auxiliary photoinitiator, ATRP initiator and SET-LRP initiator in polymerization reaction and resin preparation. The invention also discloses a preparation method for obtaining the compound through N-alkylation reaction of substituted benzophenone and secondary amine. The invention also discloses the application of the compound of the structural formula (I) as an ATRP initiator and a SET-LRP initiator in living free radical polymerization. The invention also discloses the application of the compound of the structural formula (I) as a photoinitiator and an auxiliary photoinitiator in the preparation of photocurable resins, which has a good application prospect.

Description

A kind of synthetic method and application of Michler's ketone photoinitiator

technical field

The invention relates to the field of chemistry, in particular to the synthesis of a Michler's ketone photoinitiator and its application in polymerization.

Background technique

Photocuring technology refers to the process of polymerization, crosslinking and curing of liquid phase system in a short period of time under the radiation of light. Compared with other curing methods, the advantages of light curing are: 1) fast and efficient, saving production time; 2) saving energy and meeting the requirements of green chemistry; 3) suitable for industrial production.

Traditional photocuring technology also has some deficiencies, for example, traditional photoinitiators are generally organic small molecule compounds, and these small molecule photoinitiators have the following deficiencies during use: 1) small molecule photoinitiators are often combined with polymers Poor compatibility affects its initiation efficiency; 2) It remains in the polymer after polymerization, which is easy to migrate and volatilize, resulting in odor and toxicity; 3) The surface migration of small molecule photoinitiators is also easy to cause yellowing of the polymer; 4 ) common small molecule water-based photoinitiator will affect the water resistance of resin; It is also easy to migrate and volatilize completely, producing odor and toxicity. Therefore, in recent years, people have begun to study and develop macromolecular photoinitiators and reactive photoinitiators to overcome the shortcomings of small molecular photoinitiators.

Living radical polymerization has attracted much attention in recent years because of its mild reaction conditions, wide application range of monomers, adaptability to different reaction systems, controllable product structure and molecular weight, and ability to prepare polymers with various topological structures. Among them, atom transfer radical polymerization (ATRP) has become a research hotspot in living radical polymerization due to its wide range of applicable monomers, easy availability of catalysts, easy design of initiator structure, moderate reaction temperature, and no need for traditional initiators. Another similar single-electron transfer living radical polymerization (SET-LRP), due to the low reaction temperature (polymerization can be carried out at room temperature or even lower temperature), less catalyst consumption, fast polymerization rate, and the ability to obtain ultra-high molecular weight The linear polymers, used monomers, solvents, ligands, etc. can be directly used for polymerization without purification, and this type of reaction has also been extensively studied in recent years.

Contents of the invention

The purpose of the present invention is to provide a Michler's ketone photoinitiator and its synthesis method and application.

The molecular structure general formula (I) of Michler's ketone photoinitiator of the present invention is as follows:

      

Wherein, A is H, XCH ₂ -, or -CH ₂ NR ₂ ; where X is chlorine, bromine, iodine or mercapto;

R is an alkyl or cycloalkyl group between C ₁ -C ₁₀ , phenyl, allyl, 2-hydroxyethyl, 2-(acryloyloxy)ethyl, 2-(methacryloyloxy) ) ethyl, 2-(2-bromoisobutyryloxy) ethyl, 2-(2-bromopropionyloxy) ethyl, 2-(2-chloroisobutyryloxy) ethyl, 2- (2-chloropropionyloxy)ethyl.

In the compound of molecular structure formula (I), A can be in the ortho, para or meta positions.

The synthetic method of Michler's ketone photoinitiator of the present invention is as follows:

The compound of structural formula (II) Carry out a substitution reaction with a halogenating reagent under appropriate reaction conditions to obtain a compound of structural formula (III).

      

In compounds of formula (II), G is hydrogen or methyl. In the compound of formula (III), J is hydrogen, XCH ₂ -, wherein X is chlorine, bromine, iodine or mercapto as defined in compound (I);

Compounds of formula (III) and compounds of formula (IV) React under basic conditions to obtain the product (I), wherein R is defined as an alkyl or cycloalkyl group between C ₁ -C ₁₀ in the structural formula (I), phenyl, allyl, 2-hydroxyethyl , 2-(acryloyloxy)ethyl, 2-(methacryloyloxy)ethyl, 2-(2-bromoisobutyryloxy)ethyl, 2-(2-bromopropionyloxy ) ethyl, 2-(2-chloroisobutyryloxy)ethyl, 2-(2-chloropropionyloxy)ethyl.

When the compound of structural formula (III) reacts with the compound of structural formula (IV), used base can be but not limited to sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, potassium phosphate, trimethylamine, triethylamine, Diisopropylethylamine, pyridine, pyrazine, N,N-dimethylaniline, N,N-diethylaniline, N-ethylpiperidine, N,N-dimethyldodecylamine , N, N, N', N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethylenetetramine, N,N-dimethylethanolamine, 2,2'-linked Pyridine, 4,4'-bipyridine.

When the compound of structural formula (III) reacts with the compound of structural formula (IV), the solvent used can be but not limited to water, acetone, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, acetonitrile, Tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, or a mixture of several solvents. The reaction temperature can be from -10°C to the reflux temperature of the solvent, preferably room temperature.

For the product of structural formula (I), when the group A is XCH ₂ -, the present invention also provides the application of compound (I) as ATRP initiator and SET-LRP initiator in the preparation of resin by living radical polymerization. The prepared resin can be used as macromolecular Michler's ketone photoinitiator or oligomer to directly participate in the photocuring polymerization reaction.

When compound (I) is used as an ATRP initiator for living free radical polymerization, the monomers used can be selected from one or more of acrylic compounds, methacrylic compounds, and styrene compounds; the acrylic compound monomers Including sodium acrylate, acrylate ester, among which the ester can be methyl ester, ethyl ester, allyl ester, etc. C ₁ -C ₂₀ alkyl monohydric alcohol, dihydric alcohol and polyol ester with or without cycloalkyl substitution . The methacrylic compound monomer includes sodium methacrylate, methacrylate, wherein the ester can be methyl ester, ethyl ester, allyl ester, etc., which have cycloalkyl substitution or no cycloalkyl substitution _{. -C20} alkyl monohydric alcohol, dihydric alcohol and polyol ester; styrenic compound monomers include styrene, substituted styrene, where the substituent can be in the ortho, para and meta positions, and can be monovalent or polyvalent Substitution, the substituent can be C ₁ -C ₁₈ alkyl, cycloalkyl, carboxyl or sulfonic acid group.

When the compound (I) is used as a SET-LRP initiator for living radical polymerization, the monomers used can be selected from one or more of acrylic compounds, methacrylic compounds, and styrene compounds. The acrylic monomer includes sodium acrylate and acrylate ester, wherein the ester can be a C ₁ -C ₂₀ alkyl monohydric alcohol with or without cycloalkyl substitution such as methyl ester, ethyl ester, and allyl ester, Diols and polyol esters. The methacrylic monomers include sodium methacrylate and methacrylate esters, wherein the esters can be methyl esters, ethyl esters, allyl esters, etc. with cycloalkyl substitution or without cycloalkyl substitution C ₁ - _C20 alkyl monoalcohols, diols and polyol esters; styrenic monomers include styrene, substituted styrenes, where the substituents can be in the ortho, para and meta positions, and can be mono or polysubstituted, The substituents may be C ₁ -C ₁₈ alkyl, cycloalkyl, carboxyl or sulfonic acid.

When compound (I) is used as an ATRP initiator or SET-LRP initiator for living radical polymerization, the ligands used can be selected from nitrogen-forming or phosphorus-forming ligands. Wherein the nitrogen ligand can be but not limited to 2,2'-bipyridine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, tris(2- Dimethylaminoethyl)amine, triethylenediamine (DABCO), 1,8-diazabicycloundec-7-ene (DBU), hexamethylenetetramine, N,N-dimethyl dodecylamine. The phosphorous ligand may be, but not limited to, triphenylphosphine, tris(4-methylphenyl)phosphine, tris(4-methoxyphenyl)phosphine.

When compound (I) is used as an ATRP initiator for living free radical polymerization, the catalyst used may be but not limited to CuCl, CuBr, CuCl ₂ , CuBr ₂ , FeCl ₂ , FeCl ₃ , FeBr ₂ , FeBr ₃ . When the catalyst is high-valent metal halide CuCl ₂ , CuBr ₂ , FeCl ₃ , FeBr ₃ , a reducing agent needs to be added in the reaction, and the reducing agent used can be but not limited to ascorbic acid, sodium ascorbate, glucose, hydrazine hydrate, and stannous octoate.

When the compound (I) is used as a SET-LRP initiator for living radical polymerization, the catalyst used may be Cu(0) or Fe(0).

The compound (I) is used as an ATRP initiator or a SET-LRP initiator to carry out living radical polymerization, which can be bulk polymerization, emulsion polymerization, solution polymerization, or suspension polymerization. The solvent or medium of the polymerization reaction can be but not limited to water, tetrahydrofuran, acetone, 2-butanone, acetonitrile, benzonitrile, phenylacetonitrile, benzene, toluene, xylene, ethylene glycol dimethyl ether, 1,4 - dioxane, N,N-dimethylformamide, dimethylsulfoxide, methanol, ethanol, isopropanol.

Compound (I) carries out living free radical polymerization as ATRP initiator or SET-LRP initiator, and prepared resin has following structural formula (V):

      

In the polymkeric substance of structural formula (V), R and X are as defined in structural formula (I); J ¹ represents a kind of in phenyl, sodium carboxylate or carboxylate, and wherein the ester moiety can be methyl ester, C ₁ -C ₁₈ alkyl monohydric alcohol, dihydric alcohol and polyol ester with or without cycloalkyl substitution such as ethyl ester; J ² represents one of phenyl, sodium carboxylate or carboxylate , and the ester group part can be methyl ester, ethyl ester and other C ₁ -C ₁₈ alkyl monoalcohols, diols and polyols with cycloalkyl substitution or no cycloalkyl substitution; J ³ represents phenyl , sodium carboxylate or carboxylate, and the ester group part can be methyl ester, ethyl ester, etc. with or without cycloalkyl substitution of C ₁ -C ₁₈ alkyl monohydric alcohols, Diols and polyol esters; J ¹ , J ² and J ³ can be the same group or different groups; E ¹ represents methyl or hydrogen; E ² represents methyl or hydrogen; E ³ represents methyl Or hydrogen; E ¹ , E ² and E ³ may be the same group or different groups. r=0-1000; u=0-1000; v=0-1000; y=0-1000; but r, u and y cannot be zero at the same time.

The Michler's ketone photoinitiator of the invention has simple synthesis method, convenient operation and mild reaction conditions, and has broad application prospects in the preparation of photocurable resins.

Detailed ways

The present invention is further set forth below in conjunction with embodiment. All the examples are only used to illustrate the present invention, not to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are all in accordance with conventional conditions, or in accordance with the conditions provided or suggested by the manufacturer.

Example 1 The synthesis of 4,4'-bis(chloromethyl)benzophenone (compound III-a):

In a 50ml flask, add 2.10g (10mmol) 4,4'-dimethylbenzophenone and N-chlorosuccinimide (4.01g, 30mmol), dissolve in 20mL carbon tetrachloride under heating , then azobisisobutyronitrile (0.1 g) was added. The reaction was refluxed while irradiating with 365 nm UV light. After 5 hours, the reaction was stopped. Add water and stir, separate the liquids, extract the organic phase with carbon tetrachloride, combine the organic phases, and dry over anhydrous sodium sulfate. Finally, the solvent was evaporated to obtain the crude product. Recrystallization from methanol gave the product (2.46 g, 88%).

M.p.82-83°C (the thermometer is not corrected);

¹ H NMR (CDCl ₃ ): δ7.85-7.82(m, 4H), 7.73-7.70(m, 2H), 7.67-7.55(m, 1H), 7.54-7.52(m, 2H), 6.71(s, 1H).

Example 2 Synthesis of 4-(bromomethyl)-4'-[two (2-hydroxyethyl) aminomethyl]benzophenone (compound I-a):

Dissolve 2.5g (6.79mmol) of 4,4'-bis(bromomethyl)benzophenone in 40ml of tetrahydrofuran and add it to a 100ml three-necked flask. Dissolve 0.50g (5.32mmol) of diethanolamine in 5ml of tetrahydrofuran and add The constant pressure dropping funnel was heated to 60°C and refluxed, and then 0.69 g (6.79 mmol) of triethylamine was added to the three-necked flask, and diethanolamine dissolved in tetrahydrofuran was started to be added dropwise. After the addition, the reaction was continued for 1.5h. The solvent was removed by rotary evaporation, and the residual oil was the product (1.92 g, 72.1%).

¹ H NMR (CDCl ₃ ): δ7.79-7.71 (m, 4H), 7.51-7.39 (m, 4H), 4.51 (s, 2H), 3.77 (s, 2H), 3.62 (s, 4H), 2.71 (s, 4H).

Example 3 The synthesis of 4-[two (2-hydroxyethyl) aminomethyl] benzophenone (compound I-b):

4-(Bromomethyl)benzophenone (0.28 g, 1 mmol) was dissolved in dichloromethane (20 mL), then sodium hydride (0.2 g, 5 mmol) and diethanolamine (0.21 g, 2 mmol) were added. The reaction was stirred at room temperature for 24 hours. Dichloromethane was distilled off, and water was added to the residue, followed by extraction three times with ethyl acetate. The organic phases were combined, and the organic phase was washed once with 2M hydrochloric acid, and the solvent was evaporated to obtain the product (0.25 g, 82%).

¹ H NMR (CDCl ₃ ): δ7.74-7.72(m, 4H), 7.57-7.53(m, 1H), 7.46-7.41(m, 4H), 3.78(s, 2H), 3.64(t, 4H, J=5.2Hz), 3.51 (s, br, 2H), 2.71 (t, 4H, J=5.2Hz). ¹³ C-NMR (CDCl ₃ ): δ196.5, 143.6, 137.6, 136.6, 132.4, 130.3, 130.0, 128.9, 128.3, 59.6, 58.9, 55.8.

Example 4 The synthesis of 4-[two (allyl) aminomethyl] benzophenone (compound I-c):

4-Chloromethylbenzophenone (2.3 g, 10 mmol) was dissolved in acetone/water (9:1, v:v) mixed solvent. Sodium carbonate (3.18 g, 30 mmol) was then added. A solution of diallylamine (1.9 g, 20 mmol) in acetone was slowly added to the preceding mixture at room temperature. The reaction was stirred overnight. After the reaction was completed, the reaction solution was extracted three times with dichloromethane, and the organic phases were combined, washed once with dilute hydrochloric acid, water, and saturated brine, and dried over anhydrous magnesium sulfate. Finally, the solvent was evaporated to obtain the product (2.3 g, 78%).

¹ H-NMR (CDCl ₃ ): δ7.80-7.75 (m, 4H), 7.56-7.53 (m, 1H), 7.48-7.44 (m, 4H), 5.91-5.82 (m, 2H), 5.22-5.13 (m, 4H), 3.64 (s, 2H), 3.09 (d, 4H, J=6.4Hz). ¹³ C-NMR (CDCl ₃ ): δ196.3, 144.9, 137.9, 136.5, 135.6, 132.2, 130.9, 130.7, 128.8, 128.2, 117.6, 57.3, 56.6.

Example 5 The synthesis of 4,4'-two [two (allyl) aminomethyl] benzophenone (compound I-d):

4,4'-bis(bromomethyl)benzophenone (3.68 g, 10 mmol) was dissolved in tetrahydrofuran/water (4:1, v:v) mixed solvent. Sodium carbonate (6.36 g, 60 mmol) was then added. A tetrahydrofuran solution of diallylamine (3.8 g, 40 mmol) was slowly added to the preceding mixture at room temperature. After the reaction solution was stirred for 24 hours, it was extracted three times with ethyl acetate, and the organic phases were combined, washed once with dilute sulfuric acid, water, and saturated brine, and dried over anhydrous magnesium sulfate. Finally, the solvent was evaporated to obtain the product (2.84 g, 71%).

¹ H-NMR (CDCl ₃ ): δ7.65-7.63 (m, 4H), 7.34-7.32 (m, 4H), 5.79-5.72 (m, 4H), 5.11-5.01 (m, 8H), 3.52 (s , 4H), 2.97 (d, 8H, J=6.0Hz). ¹³ C-NMR (CDCl ₃ ): δ196.1, 144.7, 136.4, 135.6, 130.1, 128.5, 117.6, 57.3, 56.6.

Example 6 Prepare polymethyl methacrylate with 4-(bromomethyl)-4'-[two (2-hydroxyethyl) aminomethyl] benzophenone (compound I-a) as AGET ATRP initiator:

Under the protection of nitrogen, compound Ia (0.2g, 0.5mmol), methyl methacrylate (5.0g, 50mmol), tetramethylethylenediamine (0.12g, 1mmol), CuBr ₂ (0.22g, 1mmol) were dispersed in toluene. After raising the reaction temperature to 60°C, 50% hydrazine hydrate (0.32 g) was added. Heat preservation reaction for 6 hours. After cooling, excess methanol was added to the reaction liquid to form a precipitate, which was filtered, and the resulting solid was dissolved in tetrahydrofuran, and purified by an aluminum peroxide column to obtain the product (4.31 g), with a monomer conversion rate of 82%.

The molecular weight M _n =7630 was determined by GPC.

Example 7 Prepare polymethyl methacrylate with 4-(bromomethyl)-4'-[two (2-hydroxyethyl) aminomethyl] benzophenone (compound I-a) as SET-LRP initiator:

Under nitrogen protection, compound I-a (0.2g, 0.5mmol), methyl methacrylate (10.0g, 100mmol), 2,2'-bipyridine (0.16g, 1mmol), Cu powder (0.064g, 1mmol) Dispersed in dimethyl sulfoxide. After raising the reaction temperature to 50° C., the reaction was incubated for 4 hours. After cooling, excess ethanol was added to the reaction solution to form a precipitate, which was filtered to obtain the product (9.21 g), with a monomer conversion rate of 92%.

The molecular weight M _n =17860 was determined by GPC.

Example 8 Preparation of allyl methacrylate and acrylic acid with 4-(bromomethyl)-4'-[bis(2-hydroxyethyl)aminomethyl]benzophenone (compound I-a) as AGET ATRP initiator Butyl ester copolymer:

Under nitrogen protection, compound Ia (0.2g, 0.5mmol), allyl methacrylate (6.31g, 50mmol), butyl acrylate (2.56g, 20mmol), pentamethyldiethylenetriamine (0.17 g, 1 mmol), FeBr ₃ (0.296 g, 1 mmol) were dispersed in acetonitrile. After raising the reaction temperature to 70°C, 50% hydrazine hydrate (0.32 g) was added. Heat preservation reaction for 8 hours. After cooling, excess methanol was added to the reaction solution to generate a precipitate, which was filtered, and the resulting solid was dissolved in tetrahydrofuran, and purified by an aluminum peroxide column to obtain a copolymer of allyl methacrylate and butyl acrylate (P(BA-co-AMA)) ( 6.74g).

The molecular weight M _n =12380 was determined by GPC.

Embodiment 9 Allyl methacrylate and butyl acrylate copolymer (P(BA-co-AMA)) prepared in embodiment 8 are photocured:

Copolymer of allyl methacrylate and butyl acrylate (P(BA-co-AMA)) (1.0 g) and ethylene glycol diacrylate (0.2 g) were dissolved in acetone and uniformly coated on a glass plate. Irradiate with a 365 nm UV lamp. After 10 minutes, a cured film was formed.

Claims (5)

1. a michaelis ketone photoinitiator for functionalization, is characterized in that: its general formula of molecular structure is such as formula (I):

Wherein, A can at ortho position, contraposition or a position be H, XCH ₂-or-CH ₂nR ₂; Wherein X is chlorine, bromine, iodine or sulfydryl;

R is C ₁-C ₁₀between alkyl, cycloalkyl, phenyl, allyl group, 2-hydroxyethyl, 2-(acryloxy) ethyl, 2-(methacryloxy) ethyl, 2-(2-bromine isobutyl acyloxy) ethyl, 2-(2-bromine propionyloxy) ethyl, 2-(2-chlorine isobutyl acyloxy) ethyl, 2-(2-chlorine propionyloxy) ethyl.

2. a michaelis ketone photoinitiator synthetic method as claimed in claim 1 is:

Structural formula (III) compound with there is structural formula (IV) secondary amine react in the basic conditions, obtain target compound (I); Wherein, J is hydrogen, XCH ₂-; X is chlorine, bromine, iodine or sulfydryl; R is C ₁-C ₁₀between alkyl, cycloalkyl, phenyl, allyl group, 2-hydroxyethyl, 2-(acryloxy) ethyl, 2-(methacryloxy) ethyl, 2-(2-bromine isobutyl acyloxy) ethyl, 2-(2-bromine propionyloxy) ethyl, 2-(2-chlorine isobutyl acyloxy) ethyl, or 2-(2-chlorine propionyloxy) ethyl.

3. michaelis ketone photoinitiator synthetic method according to claim 2, it is characterized in that: alkali used is sodium carbonate, salt of wormwood, cesium carbonate, sodium hydroxide, potassium hydroxide, potassiumphosphate, Trimethylamine 99, triethylamine, diisopropyl ethyl amine, pyridine, pyrazine, N, accelerine, N, N-Diethyl Aniline, N-ethylpiperidine, N, N-dimethyl dodecylamine, N, N, N ', N '-Tetramethyl Ethylene Diamine, five methyl diethylentriamine, vulkacit H, N, N-dimethylethanolamine, 2,2 '-dipyridyl, 4,4 '-dipyridyl;

Solvent for use is the solvent mixture of water, acetone, methylene dichloride, 1,2-ethylene dichloride, chloroform, tetracol phenixin, acetonitrile, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, benzene,toluene,xylene or several solvent; Temperature of reaction is-10 DEG C of reflux temperatures to solvent, preferred room temperature.

4. michaelis ketone photoinitiator formula (I) according to claim 1 the application that living free radical polymerization prepares resin is carried out as ATRP initiator or SET-LRP initiator; The A of described (I) is XCH ₂-;

In living free radical polymerization, part used is selected from nitrogenous or phosphorus-containing ligand; Wherein containing n-donor ligand is 2,2 '-bipyridine, N, N, N ', N '-Tetramethyl Ethylene Diamine, five methyl diethylentriamine, three (2-dimethylaminoethyl) amine, triethylenediamine (DABCO), 1,8-diazabicylo 11 carbon-7-alkene (DBU), vulkacit H or N, N-dimethyl dodecylamine; Phosphorus-containing ligand is triphenylphosphine, three (4-aminomethyl phenyl) phosphines or three (4-p-methoxy-phenyl) phosphine;

When compound (I) carries out living free radical polymerization as ATRP initiator, used catalyst is CuCl, CuBr, CuCl ₂, CuBr ₂, FeCl ₂, FeCl ₃, FeBr ₂, FeBr ₃; When catalyzer is CuCl ₂, CuBr ₂, FeCl ₃, FeBr ₃time, need in reaction to add reductive agent xitix, sodium ascorbate, glucose, hydrazine hydrate, stannous octoate;

When compound (I) carries out living free radical polymerization as SET-LRP initiator, used catalyst is Cu (O) or Fe (O).

5. apply obtained resin described in claim 4, there is structure formula V:

J ¹represent the one in phenyl, carboxylic acid sodium or carboxylicesters, and Ester groups wherein can be methyl esters, ethyl ester etc. have cycloalkyl substituted or do not have the C of cycloalkyl substituted ₁-C ₁₈alkyl monocarbon alcohol, dibasic alcohol and polyol ester; J ²represent the one in phenyl, carboxylic acid sodium or carboxylicesters, and Ester groups wherein can be methyl esters, ethyl ester etc. have cycloalkyl substituted or do not have the C of cycloalkyl substituted ₁-C ₁₈alkyl monocarbon alcohol, dibasic alcohol and polyol ester; J ³represent the one in phenyl, carboxylic acid sodium or carboxylicesters, and Ester groups wherein can be methyl esters, ethyl ester etc. have cycloalkyl substituted or do not have the C of cycloalkyl substituted ₁-C ₁₈alkyl monocarbon alcohol, dibasic alcohol and polyol ester; J ¹, J ²with J ³for identical group also can be different group; E ¹represent methyl or hydrogen; E ²represent methyl or hydrogen; E ³represent methyl or hydrogen; E ¹, E ²with E ³can be identical group also can be different groups; R=0-1000; U=0-1000; V=0-1000; Y=0-1000; But r, u, y can not be zero simultaneously.