CN105482043A - Acrylate polymer, preparation method and application of acrylate polymer - Google Patents

Abstract

The invention discloses an acrylate polymer. The acrylate polymer contains a following repetition structure unit represented in the specification, wherein n is 5-13, and R is selected from C1-C6 alkyl groups. The invention further discloses a preparation method of the acrylate polymer. The preparation method comprises steps as follows: prepolymer MCE monomers containing glycidyl tertiary carboxylic ester and acrylic monomers as well as a mixture of acrylate monomers and an initiator are dropwise added to a solvent under the protection of nitrogen, a product is subjected to the primary heat preservation, and the initiator is supplemented; then the heat preservation is performed for the second time, and finally, the solvent is added for dilution and adjustment of solids, so that the acrylate polymer is obtained. The monomers containing anchor groups are introduced and contain a certain number of carbon chains, terminal groups contain the anchor groups, resin molecular chains containing the anchor groups are close to CAB (cellulose acetate butyrate) molecular chains, and the molecular chains are interwoven and anchored and are not prone to falling off, so that the compatibility of acrylic resin and CAB resin is good.

Description

A kind of acrylic ester polymer, preparation method and its usage

Technical field

The invention belongs to technical field of coatings, particularly relate to a kind of coating acrylic ester polymer, the preparation method and its usage good with cellulose acetate butyrate consistency.

Background technology

China has become automobile market maximum in the world, and in 10 years of future, along with the increase of car owning amount, car refinishing paint will become the fastest-rising coating variety of Chinese coating industry.Due to acrylic resin of light color, outdoor weatherability is good, protect that look gloss retention is excellent, nondiscoloration under overbaking (lower than 170 DEG C), have certain solidity to corrosion, these characteristics determine the popularity of acrylic coating application.

At present, maximum market is automobile (especially car) application.Cellulose acetate butyrate (CAB) is the cellulosic esterification products of natural polymer.Have the advantages such as the oriented alignment of good water tolerance, weathering resistance, film-forming flexibility, heigh clarity and energy stable metal due to cellulose acetate butyrate, therefore cellulose acetate butyrate is widely used in automobile finish.In the priming paint of automobile, CAB's adds the orientation impelling priming paint contraction and al powder flake when contributing to solvent evaporates as much as possible; In the coating varnish of automobile, select the CAB of different butyryl radicals content, after finishing varnish can be made to coat, avoid solvent to be penetrated into bottom, thus make automobile finish light attractive in appearance; CAB, in car refinishing paint system, can shorten time of drying, improves cold-crack resistance, and has good polishing performance.

CAB commercially available is at present U.S. EASTMAN Products, wherein has the product of a series of trade mark according to the content of butyryl acyloxy and the size of viscosity, as CAB-551-0.01, CAB-381-0.5, CAB-381-2 etc.The kind that content is high and viscosity is less of butyryl acyloxy is as CAB-551-0.01, better by acrylic resin consistency with coating, but dryness is with relative poor to the arrangement effect of aluminium powder; The kind that the content of butyryl acyloxy is low and viscosity is larger is as CAB-381-2, poor with coating acrylic resin consistency, but dryness and better to the arrangement effect of aluminium powder.

The car refinishing paint obtained by acrylic resin and cellulose acetate butyrate blending and modifying has the two advantage, obtains good performance.But cellulose acetate only in very strong solvent as there is solvability in acetone, butanone and acetic acid second vinegar; And have very low varsol tolerance, very poor with the matching of resin, the commercial resins that can coordinate with it is also few.If acrylic resin and cellulose acetate butyrate consistency bad, the performance of coating can be had a strong impact on, film coated surface gloss difference, wrinkling, have a strong impact on aluminium powder arrangement.

In view of this, be necessary to provide a kind of coating acrylic ester polymer good with cellulose acetate butyrate consistency.

Summary of the invention

For the defect of prior art, the object of this invention is to provide a kind of coating acrylic ester polymer good with cellulose acetate butyrate consistency.

Another object of the present invention is to provide a kind of preparation method of aforesaid propylene acid ester polymer.

Another object of the present invention is to provide the purposes that a kind of aforesaid propylene acid ester polymer is used as coating.

In order to realize described object, the technical solution used in the present invention is as follows:

A kind of acrylic ester polymer, has following repeated structural unit:

N=5 ~ 13, R is selected from C ₁~ C ₆alkyl.

The number-average molecular weight Mn of described acrylic ester polymer is 4500 ~ 9500, weight-average molecular weight Mw is 20000 ~ 60000, and dispersity Mw/Mn is 3 ~ 8, and glass transition temperature Tg is 4 ~ 64 DEG C, hydroxyl value is 40 ~ 80mgKOH/g, solubility parameter SP is 10.2 ~ 10.55.

A preparation method for described acrylic ester polymer, comprises the following steps:

Under nitrogen protection, MCE monomer is dripped: the prepolymer of tertiary carbonic acid glycidyl ester and Acrylic Acid Monomer is (hereinafter referred to as MCE monomer in solvent, M:MAA methacrylic acid, CE:CARDURAE10P), the mixture of acrylate monomer and initiator, first time insulation, adds initiator; Then second time insulation, finally adds solvent and carries out dilution adjustment solid part thus obtain acrylic ester polymer.

The consumption of described initiator is 1 ~ 3% of acrylate monomer weight.

The consumption of described MCE monomer accounts for 16 ~ 20% of MCE monomer, acrylate monomer, initiator and solvent total mass.

The consumption of described solvent accounts for 50 ~ 55% of MCE monomer, acrylate monomer, initiator and solvent total mass.

The temperature of the mixture of described dropping MCE monomer, acrylate monomer and initiator is 100 ~ 115 DEG C.

3 ~ 5 hours mixture used times (h) of described dropping MCE monomer, acrylate monomer and initiator.

The time of described first time insulation is 0.5 ~ 1 hour (h).

Describedly add 1.5 ~ 2.0 hours initiator used times (h).

The time of described second time insulation is 1.5 ~ 2.5 hours (h).

Described solid part is 50 ~ 55%.

Described acrylate monomer can be at least one in vinylbenzene, ethyl propenoate, methyl acrylate, methyl methacrylate, n-butyl acrylate, isobornyl acrylate, lauryl methacrylate(LMA); Containing carboxyl functional monomer: as at least one in methacrylic acid, vinylformic acid; Hydroxy functional groups monomer: as at least one in hydroxyethyl methylacrylate, Rocryl 410, Propylene glycol monoacrylate, Hydroxyethyl acrylate.

Described initiator is peroxide type initiators, be preferably at least one in benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methylethyl ketone peroxide, tert-butyl peroxide 2-ethylhexyl, peroxidation acetic acid tert-pentyl ester, two t-amyl peroxy compounds, peroxidation 2 ethyl hexanoic acid tert-pentyl ester, be more preferably peroxidation 2 ethyl hexanoic acid tert-pentyl ester.

Described solvent can be at least one in esters solvent, benzene kind solvent, and wherein: esters solvent can select at least one in N-BUTYL ACETATE, 1-Methoxy-2-propyl acetate, benzene kind solvent then can select at least one in toluene, dimethylbenzene.

Described MCE monomer: the structural formula of the prepolymer (hereinafter referred to as MCE monomer, M:MAA methacrylic acid, CE:CARDURAE10P) of tertiary carbonic acid glycidyl ester and Acrylic Acid Monomer is as follows:

Wherein: R ₁+ R ₂carbon atom number be 7; R ₁and R ₂be selected from C ₁~ C ₆alkyl.

The preparation method of described MCE monomer, comprises the following steps:

Tertiary carbonic acid glycidyl ester is dissolved in solvent, carboxylic Acrylic Acid Monomer is instilled in described tertiary carbonic acid glycidyl ester solution, under the protection of stopper, the obtained monomer of reaction under high temperature.

Described carboxylic Acrylic Acid Monomer is at least one in vinylformic acid, methacrylic acid, is preferably methacrylic acid.

The consumption of described carboxylic Acrylic Acid Monomer is 1 ~ 1.2 times of tertiary carbonic acid glycidyl ester equivalent.

Described stopper is phenolic inhibitor, is preferably at least one in Resorcinol, tert-butyl catechol, Pyrogentisinic Acid's monobutyl ether, is more preferably Resorcinol; Consumption accounts for 0.05% of carboxylic Acrylic Acid Monomer weight.

Described solvent is at least one in esters solvent, benzene kind solvent; Wherein, esters solvent is N-BUTYL ACETATE, and benzene kind solvent is at least one in toluene, dimethylbenzene, and adjustment solid part is 70 ~ 90%.

The temperature of described reaction is 140 ~ 150 DEG C; Reaction end is judged 15 ~ 35 by controlling acid number.

A kind of aforesaid propylene acid ester polymer is used as the purposes of coating.

Owing to adopting described technical scheme, the present invention has the following advantages and beneficial effect:

The present invention introduces the monomer containing anchoring group, this particular monomers has certain carbochain number, end group has anchoring group, molecular resin chain containing this anchoring group and cellulose acetate butyrate (CAB) molecular chain close, molecular chain is wound around and grappling mutually, difficult drop-off, thus make acrylic resin and CAB resin compatible good.

Introduce anchoring group in the present invention, improve the consistency between the larger resin of these two kinds of molecular structures differences of acrylic resin and cellulose acetate butyrate greatly, also can improve the gloss of film, fullness ratio, clarity simultaneously; By the design of the technical parameter (molecular weight, second-order transition temperature, solubility parameter and hydroxyl value) to acrylic resin, obtain a parameter area value: number-average molecular weight is Mn=4500 ~ 9500, weight-average molecular weight Mw=20000 ~ 60000, dispersity Mw/Mn is 3 ~ 8; Solubility parameter (SP value) is 10.2 ~ 10.55; Second-order transition temperature (Tg value) is 4 ~ 64 DEG C; Hydroxyl value is 40 ~ 80mgKOH/g.The acrylic resin of different performance can be prepared as required, the consistency had with cellulose acetate butyrate CAB-381-2 in described value range; Can be applied in thermoplastic acrylic resin and baking-type acrylic resin further; Painting except being applied in car repair, also can be widely used in other and can use in the coating of cellulose acetate butyrate and acrylic resin; As the varnish of transparent metal varnish, Plastic, the varnish, amino-stoving varnish, vehicle paint base, metal flash paint, ultraviolet-curing paint etc. of timber.

Embodiment:

Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.Those of ordinary skill in the art should be appreciated that hereinafter provided embodiment is not used for limiting the scope that contains of the present invention.

The testing method of the solubility parameter SP in the present invention is as follows:

The testing method of solubility parameter SP is: the polyester sample acetone diluted of 10 grams of getting 0.5 gram, is then placed in 20 DEG C of cleansing bath tubs, uses normal hexane and deionized water titration respectively by sample beaker, until become muddy.

Solubility parameter SP calculation formula is as follows:

$SP=\sqrt{\frac{\sqrt{Vml}*{\mathrm{\δ}}^{2}ml+\sqrt{Vmh}*{\mathrm{\δ}}^{2}mh}{\sqrt{Vml}+\sqrt{Vmh}}}$

Wherein:

$\begin{array}{cc}Vml=\frac{V\left(Hexane\right)*Vg}{\mathrm{\φ}ml*Vg+(1-\mathrm{\φ}ml)*V\left(hexane\right)}& Vmh=\frac{V\left(water\right)*Vg}{\mathrm{\φ}mh*Vg+(1-\mathrm{\φ}mh)*V\left(water\right)}\end{array}$

Vml, Vmh are the molecular volume of each solvent,

The molecular volume that V (Hexane) is normal hexane (hexane),

The molecular volume that V (Water) is deionized water (water),

Vg is the molecular volume of good solvent acetone,

$\begin{array}{cc}\mathrm{\φ}ml=\frac{T\left(Hexane\right)}{10+T\left(Hexane\right)}& \mathrm{\φ}mh=\frac{T\left(Water\right)}{10+T\left(Water\right)}\end{array}$

The volume fraction of normal hexane (hexane) when Φ ml is for dripping to terminal,

The volume fraction of deionized water (water) when Φ mh is for dripping to terminal,

The volume of normal hexane (hexane) when T (Hexane) is for dripping to terminal,

The volume of deionized water (water) when T (water) is for dripping to terminal,

$\mathrm{\δ}ml=\sqrt{\mathrm{\φ}ml*{\mathrm{\δ}}^2\left(Hexane\right)+(1-\mathrm{\φ}ml){\mathrm{\δ}}^{2}g}$

$\mathrm{\δ}mh=\sqrt{\mathrm{\φ}mh*{\mathrm{\δ}}^2\left(Water\right)+(1-\mathrm{\φ}mh){\mathrm{\δ}}^{2}g}$

δ ml, δ mh are the solubility parameter SP of each solvent when dripping to terminal,

The solubility parameter SP that δ (Hexane), δ (water) are normal hexane (hexane) and deionized water (water).

δ g is the solubility parameter SP of solvent acetone.

The impact of the solubility parameter SP relative consistency of acrylic ester polymer: the parameter directly reflecting resin compatible, the SP value of two kinds of resins is more close, consistency is better, and the SP value of resin is subject to the impact of molecular resin amount, Tg value, hydroxyl value, monomer structure etc.

In following examples, the detection method of acrylic ester polymer and cellulose acetate butyrate CAB-381-2 consistency is: acrylic ester polymer and CAB-381-2 (15%) solution quality ratio=1:1, mixing until solution clear and dry film transparent.

CAB-381-2 (15%) solution formula comprises the component of following mass percent:

Butylacetate 85%,

EastmanCAB381-215％。

The impact of the second-order transition temperature relative consistency of acrylic ester polymer: acrylic ester polymer Tg is high, namely chain link rigidity is strong, and not easily move, film dryness is good, but snappiness and consistency poor; Tg is low, and namely chain link is flexible, is easy to motion, is easy to molecular chain and is mutually wound around, and consistency is better, but dryness and hardness poor.

The impact of the hydroxyl value relative consistency of acrylic ester polymer: hydroxyl is a kind of polar group, and hydrogen bond force is provided, as the hydrogen bond force of intermolecular forces, stronger effect is had to the winding stability between molecular chain and molecular chain, be conducive to the consistency of resin, but too strong hydrogen bond force plays the retroaction of repulsion on the contrary.

The molecular weight of acrylic ester polymer and molecular weight distribution: molecular weight is little, consistency is good, but Physical properties of coating film is poor; Molecular weight is large, poor compatibility, but Physical properties of coating film is good.

Embodiment 1

One, preparation is containing the monomer of anchoring group, also known as MCE monomer: the prepolymer of tertiary carbonic acid glycidyl ester and Acrylic Acid Monomer; Define name of an article MCE-BAC (methacrylic acid and tertiary carbonic acid glycidyl ester prepolymer butylacetate solution) in the present embodiment, fill a prescription as shown in table 1:

Table 1

Preparation method: be equipped with in the four-hole boiling flask of agitator, prolong, thermometer, dropping funnel to one; add CARDURAE10P57g, butylacetate 20g; 140 DEG C are warmed up under nitrogen protection; add the mixture of methacrylic acid 23g and Resorcinol 0.012g; drip and terminate follow-up continuing to be warmed up to 150 DEG C, be incubated to reaction end.Control of reaction end point detects acid number 15 ~ 35, viscosity A5-E (Gardner-Holdt bubble tube/25 DEG C) for qualified, and solid part is 70 ~ 90%, obtains the faint yellow monomer containing anchoring group.

Two, prepare acrylic ester polymer, fill a prescription as shown in table 2:

Table 2

Preparation method: be equipped with agitator to one, prolong, thermometer, in the four-hole boiling flask of dropping funnel, add butylacetate 32.15g, then under nitrogen protection, acrylate monomer (ethyl propenoate 14.45g is dripped with dropping funnel at 110 DEG C, isobornyl acrylate 3.4g, methyl methacrylate 15.74g, methacrylic acid 0.65g), the mixture 54.89g of MCE monomer (MCE-BAC20g) and initiator peroxidation 2 ethyl hexanoic acid tert-pentyl ester 0.65g, within 4 hours, dropwise, be incubated 0.5 hour, mend and drip initiator 0.4g peroxidation 2 ethyl hexanoic acid tert-pentyl ester 1.5 hours, be incubated 1.5 hours, cooling adds butylacetate 8.86g, 1-Methoxy-2-propyl acetate 3.7g, adjustment solid part is 50 ~ 55%, the MCE consumption of obtained acrylic ester polymer is 20g, molecular chain conformation is: number-average molecular weight Mn=7340, weight-average molecular weight Mw=37928, dispersity M _w/ Mn=5.17, glass transition temperature Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=50mgKOH/g, solubility parameter SP=10.46.Solid part is 51.18%, viscosity U ~ V, and acid number 8.34 is qualified with CAB-381-2 consistency.

Embodiment 2

1, prepare acrylic ester polymer, fill a prescription as shown in table 3:

Table 3

2, preparation method is with embodiment 1, and solvent is changed to butylacetate, and diluting solvent is butylacetate and 1-Methoxy-2-propyl acetate, the MCE consumption of obtained acrylic ester polymer is 16%, molecular chain conformation is: number-average molecular weight Mn=5898, weight-average molecular weight Mw=43118, dispersity M _w/ Mn=7.311, glass transition temperature Tg (theoretical value)=4 DEG C, hydroxyl value (theoretical value)=42mgKOH/g, solubility parameter SP=10.25.Solid part is 50.53%, viscosity N ~ O, and acid number 9.65 is qualified with CAB-381-2 consistency.

Comparative example 1

1, prepare acrylic ester polymer, fill a prescription as shown in table 4:

Table 4

2, preparation method is with embodiment 1, and the MCE-BAC consumption of obtained acrylic ester polymer is 12%, and molecular chain conformation is: Mn=6025, Mw=36529, M _w/ Mn=6.061, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=73.7mgKOH/g, SP=10.57.Solid part is 50.65%, viscosity Q ~ R, and acid number 10.1 is defective with CAB-381-2 consistency.

Comparative example 2

1, prepare acrylic ester polymer, fill a prescription as shown in table 5:

Table 5

2, preparation method is with embodiment 1, and the MCE-BAC consumption of obtained acrylic ester polymer is 8%, and molecular chain conformation is: Mn=6598, Mw=29830, M _w/ Mn=4.521, Tg (theoretical value)=4 DEG C, hydroxyl value (theoretical value)=74.1mgKOH/g, SP=10.59.Solid part is 50.71%, viscosity Y, and acid number 9.06 is defective with CAB-381-2 consistency.

Comparative example 3

1, prepare acrylic ester polymer, fill a prescription as shown in table 6:

Table 6

2, preparation method: be equipped with in the four-hole boiling flask of agitator, prolong, thermometer, dropping funnel to; add butylacetate 36.15g; then under nitrogen protection at 110 DEG C; monomer initiator mixture 50.19g is dripped with dropping funnel; within 4 hours, dropwise; be incubated 0.5 hour; mend and drip initiator 1.5 hours; be incubated 1.5 hours, cooling adds butylacetate 9.46g, 1-Methoxy-2-propyl acetate 3.8g; the MCE consumption of obtained acrylic ester polymer is 0; molecular chain conformation is: Mn=7307, Mw=37304, M _w/ Mn=5.106, Tg (theoretical value)=49 DEG C, hydroxyl value (theoretical value)=58mgKOH/g, SP=11.17.Solid part is 51.07%, viscosity Y ~ Z, and acid number 8.97 is defective with CAB-381-2 consistency.

Embodiment 3

1, prepare acrylic ester polymer, fill a prescription as shown in table 7:

Table 7

2, preparation method is with embodiment 1, and obtained acrylic ester polymer, molecular chain conformation is: Mn=6466, Mw=39512, Mw/Mn=5.764, Tg (theoretical value)=10.6 DEG C, hydroxyl value (theoretical value)=65mgKOH/g, SP=10.25.Solid part is 51.29%, viscosity T ~ U, and acid number 8.3 is qualified with CAB-381-2 consistency.

Embodiment 4

1, prepare acrylic ester polymer, fill a prescription as shown in table 8:

Table 8

2, preparation method is with embodiment 1, and the molecular chain conformation of obtained acrylic ester polymer is: Mn=7471, Mw=35181, M _w/ Mn=4.709, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=60mgKOH/g, SP=10.50.Solid part is 51.54%, viscosity S ~ T, and acid number 9.36 is qualified with CAB-381-2 consistency.

Comparative example 4

1, prepare acrylic ester polymer, fill a prescription as shown in table 9:

Table 9

2, preparation method is with embodiment 1, and obtained acrylic ester polymer, molecular chain conformation is: Mn=6993, Mw=36342, Mw/Mn=5.197, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=60mgKOH/g, SP=10.04.Solid part is 51.77%, viscosity L, and acid number 8.79 is defective with CAB-381-2 consistency.

Comparative example 5

1, prepare acrylic ester polymer, fill a prescription as shown in table 10:

Table 10

2, preparation method is with embodiment 1, and obtained acrylic ester polymer, molecular chain conformation is: Mn=7520, Mw=40110, Mw/Mn=5.333, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=60mgKOH/g, SP=10.64.Solid part is 51.77%, viscosity U ~ V, and acid number 9.23 is defective with CAB-381-2 consistency.

Comparative example 6

1, prepare acrylic ester polymer, fill a prescription as shown in table 11:

Table 11

2, preparation method is with embodiment 1, and obtained acrylic ester polymer, molecular chain conformation is: Mn=8564, Mw=34222, Mw/Mn=3.996, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=60mgKOH/g, SP=10.819.Solid part is 51.32%, viscosity W ~ Y, and acid number 8.73 is defective with CAB-381-2 consistency.

Embodiment 5

1, prepare acrylic ester polymer, fill a prescription as shown in table 12:

Table 12

2, preparation method is with embodiment 1, and obtained acrylic ester polymer, molecular chain conformation is: Mn=9240, Mw=36165, Mw/Mn=5.197, Tg (theoretical value)=64 DEG C, hydroxyl value (theoretical value)=60mgKOH/g, SP=10.25.It is 51.07%, viscosity Z2 that solid part is defined as, and acid number 8.72 is qualified with CAB-381-2 consistency.

Comparative example 7

1, prepare acrylic ester polymer, fill a prescription as shown in table 13:

Table 13

2, preparation method is with embodiment 1, obtained acrylic ester polymer, and molecular chain conformation is: Mn=6533, Mw=48794, Mw/Mn=7.469, Tg (theoretical value)=and-9 DEG C, hydroxyl value (theoretical value)=60mgKOH/g, SP=10.23.Solid part is 51.32%, viscosity K ~ L, and acid number 8.86 is defective with CAB-381-2 consistency.

Comparative example 8

1, prepare acrylic ester polymer, fill a prescription as shown in table 14:

Table 14

2, preparation method is with embodiment 1, and obtained acrylic ester polymer, molecular chain conformation is: Mn=7233, Mw=29024, Mw/Mn=4.013, Tg (theoretical value)=70 DEG C, hydroxyl value (theoretical value)=60mgKOH/g, SP=10.5.Solid part is 51.77%, viscosity Z ~ Z1, and acid number 9.3 is defective with CAB-381-2 consistency.

Embodiment 6

1, prepare acrylic ester polymer, fill a prescription as shown in Table 15:

Table 15

2, preparation method is with embodiment 1, and obtained acrylic ester polymer, molecular chain conformation is: Mn=4859, Mw=23657, Mw/Mn=4.869, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=50mgKOH/g, SP=10.51.Solid part is 50.17%, viscosity M ~ N, and acid number 8.92 is qualified with CAB-381-2 consistency.

Embodiment 7

1, prepare acrylic ester polymer, fill a prescription shown in table 16:

Table 16

2, preparation method is with embodiment 1, and obtained acrylic ester polymer, molecular chain conformation is: Mn=6353, Mw=32174, Mw/Mn=5.065, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=80mgKOH/g, SP=10.48.Solid part is 50.27%, viscosity R ~ S, and acid number 8.96 is qualified with CAB-381-2 consistency.

Comparative example 9

1, prepare acrylic ester polymer, fill a prescription shown in table 17:

Table 17

2, preparation method is with embodiment 1, and obtained acrylic ester polymer, molecular chain conformation is: Mn=6049, Mw=30795, Mw/Mn=5.091, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=120mgKOH/g, SP=10.41.Solid part is 50.56%, viscosity P, and acid number 9.5 is defective with CAB-381-2 consistency.

Embodiment 8

1, prepare acrylic ester polymer, fill a prescription shown in table 18:

Table 18

2, preparation method is with embodiment 1, and temperature of reaction reduces to 100 DEG C, obtained acrylic ester polymer, molecular chain conformation is: Mn=7885, Mw=57915, Mw/Mn=7.345, Tg (theoretical value)=10.6 DEG C, hydroxyl value (theoretical value)=65mgKOH/g, SP=10.25.Solid part is 51.77%, viscosity W ~ Y, and acid number 8.96 is qualified with CAB-381-2 consistency.

Embodiment 9

1, prepare acrylic ester polymer, fill a prescription shown in table 19:

Table 19

2, preparation method is with embodiment 1, and temperature of reaction is upgraded to 115 DEG C, obtained acrylic ester polymer, molecular chain conformation is: Mn=5047, Mw=21109, Mw/Mn=4.183, Tg (theoretical value)=10.6 DEG C, hydroxyl value (theoretical value)=65mgKOH/g, SP=10.25.Solid part is 51.6%, viscosity J ~ K, and acid number 8.96 is qualified with CAB-381-2 consistency.

Comparative example 10

1, prepare acrylic ester polymer, fill a prescription shown in table 20:

Table 20

2, preparation method is with embodiment 1, and temperature of reaction reduces to 100 DEG C, obtained acrylic ester polymer, molecular chain conformation is: Mn=9569, Mw=126977, Mw/Mn=13.27, Tg (theoretical value)=10.6 DEG C, hydroxyl value (theoretical value)=65mgKOH/g, SP=10.25.Solid part is 50.88%, viscosity Z1 ~ Z2, and acid number 7.91 is defective with CAB-381-2 consistency.

Embodiment 10

Dimethylbenzene is used to make solvent

One, preparation is containing the monomer of anchoring group, also known as MCE monomer: the prepolymer of tertiary carbonic acid glycidyl ester and Acrylic Acid Monomer; Define name of an article MCE (methacrylic acid and tertiary carbonic acid glycidyl ester prepolymer xylene solution) in the present embodiment, fill a prescription shown in table 21:

Table 21

Preparation method: be equipped with in the four-hole boiling flask of agitator, prolong, thermometer, dropping funnel to one; add CARDURAE10P57g, dimethylbenzene 20g; 140 DEG C are warmed up under nitrogen protection; add the mixture of methacrylic acid 23g and Resorcinol 0.012g; drip and terminate follow-up continuing to be warmed up to 150 DEG C, be incubated to reaction end.Control of reaction end point detects acid number 15 ~ 35, viscosity A5-E (Gardner-Holdt bubble tube/25 DEG C) for qualified, and solid part is 70 ~ 90%, obtains the faint yellow monomer containing anchoring group.

Two, prepare acrylic ester polymer, fill a prescription shown in table 22:

Table 22

Preparation method: be equipped with agitator to one, prolong, thermometer, in the four-hole boiling flask of dropping funnel, add dimethylbenzene 32.46g, butylacetate 8.67g, then under nitrogen protection, acrylate monomer (vinylbenzene 3.66g is dripped with dropping funnel at 110 DEG C, n-butyl acrylate 5.92g, hydroxyethyl methylacrylate 3.07g, methyl methacrylate 25.12g), MCE monomer 16g and initiator peroxidation 2 ethyl hexanoic acid tert-pentyl ester 0.396g mixture 54.166g, within 4 hours, dropwise, be incubated 0.5 hour, mend and drip initiator 0.145g peroxidation 2 ethyl hexanoic acid tert-pentyl ester 1.5 hours, be incubated 1.5 hours, cooling adds dimethylbenzene 4.559g, adjustment solid part is 50 ~ 55%, obtained acrylic ester polymer MCE consumption is 16.00%, molecular chain conformation be: Mn=8369, Mw=26735, M _w/ Mn=3.2, Tg (theoretical value)=54 DEG C, hydroxyl value (theoretical value)=65mgKOH/g, SP=10.45.Solid part is 50.17%, viscosity X ~ Y, and acid number 3.5 is qualified with CAB-381-2 consistency.

MCE monomer contains double bond, can participate in Raolical polymerizable, and simultaneously containing hydroxyl, can participate in the crosslinking reaction in later stage, its consumption is at least 16% of reactant gross weight; Result is shown in table 23:

Table 23

Title	MCE consumption %	With CAB-381-2 consistency
			Embodiment 1	20	Qualified
Embodiment 2	16	Qualified
			Comparative example 1	12	Defective
Comparative example 2	8	Defective
			Comparative example 3	0	Defective

From embodiment and comparative example, MCE consumption > 16%, can obtain and the resin qualified with CAB-381-2 consistency, but considers cost factor, and MCE dosage is 16%.

In the present invention, the solubility parameter (SP value) of acrylic ester polymer is 10.2 ~ 10.55.Fixing MCE dosage is 16%, adjusts SP value by adjustment acrylate monomer kind and ratio, investigates the impact of SP value relative consistency.Result is shown in table 24:

Table 24

Title	SP value	With CAB-381-2 consistency
			Embodiment 3	10.25	Qualified
Embodiment 4	10.5	Qualified
			Comparative example 4	10.04	Defective
Comparative example 5	10.64	Defective
			Comparative example 6	10.819	Defective

As can be known from the above table, when SP value is between 10.2 ~ 10.55, acrylic ester polymer and CAB-381-2 consistency qualified.

The second-order transition temperature (Tg value) of acrylic ester polymer is 4 ~ 64 DEG C.Fixing MCE dosage is 16%, SP value is 10.2 ~ 10.55, adjusts Tg value by adjustment acrylate monomer kind and ratio, investigates the impact of Tg value relative consistency.Result is as shown in Table 25:

Table 25

Title	Tg value (DEG C)	With CAB-381-2 consistency
			Embodiment 2	4	Qualified
Embodiment 4	34	Qualified
			Embodiment 5	64	Qualified
Comparative example 7	-9	Defective
			Comparative example 8	70	Defective

As can be known from the above table, when Tg is between 4 ~ 64 DEG C, acrylic ester polymer and CAB-381-2 consistency qualified.

The hydroxyl value of acrylic ester polymer is 40 ~ 80mgKOH/g; Fixing MCE dosage is 16%, SP value is 10.25 ~ 10.55, adjusts hydroxyl value by adjustment acrylate monomer kind and ratio, investigates the impact of hydroxyl value relative consistency.Result is shown in table 26:

Table 26

The number-average molecular weight of acrylic ester polymer is Mn=4500 ~ 9500, weight-average molecular weight Mw=20000 ~ 60000, and molecular weight distribution is 3 ~ 8.Fixing formula, by adjusting process and initiator amount, investigates the impact of molecular size range relative consistency.Result is shown in table 27:

Table 27

Title	Number-average molecular weight Mn	Weight-average molecular weight Mw	Dispersity Mw/Mn	With CAB-381-2 consistency
					Embodiment 3	6466	39512	5.764	Qualified
Embodiment 8	7885	57915	7.345	Qualified
					Embodiment 9	5047	21109	4.183	Qualified
Comparative example 10	9569	126977	13.27	Defective

As can be known from the above table, when SP value, Tg value, hydroxyl value one timing, number-average molecular weight is between 4500 ~ 9500, and the impact of molecular weight relative consistency is not very large.

Embodiment 11

Be with the difference of embodiment 1: initiator uses two t-amyl peroxy compounds, consumption is 2.5% of monomer weight, the other the same as in Example 1 consistent, acquired results is the same manner as in Example 1, obtained acrylic ester polymer MCE consumption is 16.00%, molecular chain conformation is: Mn=6678, Mw=29745, M _w/ Mn=4.5, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=65mgKOH/g, SP=10.45.Solid part is 50.08%, viscosity R ~ S, and acid number 8.5 is qualified with CAB-381-2 consistency.

Embodiment 12

Be with the difference of embodiment 1: initiator uses peroxidation acetic acid tert-pentyl ester, consumption is 2.3% of monomer weight, the other the same as in Example 1 consistent, acquired results is the same manner as in Example 1, obtained acrylic ester polymer MCE consumption is 16.00%, molecular chain conformation is: Mn=6349, Mw=29785, M _w/ Mn=4.7, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=65mgKOH/g, SP=10.40.Solid part is 50.13%, viscosity U ~ V, and acid number 8.15 is qualified with CAB-381-2 consistency.

Embodiment 13

Be with the difference of embodiment 1: initiator uses tert-butyl peroxide 2-ethylhexyl, consumption is 2.7% of monomer weight, and obtained acrylic ester polymer MCE consumption is 16.00%, and molecular chain conformation is: Mn=5386, Mw=27797, M _w/ Mn=5.2, Tg (theoretical value)=34 DEG C, hydroxyl value (theoretical value)=65mgKOH/g, SP=10.42.Solid part is 50.24%, viscosity S ~ T, and acid number 8.31 is qualified with CAB-381-2 consistency.

Embodiment 14, comparative example 11

Acrylic ester polymer embodiment 2 prepared and other company's acrylic resin are made into car refinishing paint coating varnish according to table 28, weight (g) and component shown in table 28.

Table 28

Title	Specification	Embodiment 14	Comparative example 11
				Commercially available acrylic resin (hydroxyl value=70 ~ 90, Mn=6000 ~ 8000)	Industrial goods	36.5	51.5
CAB-381-2 (15%) solution	Industrial goods	11.5	11.5
				Acrylic ester polymer prepared by embodiment 2	Own product	15	0
Butylacetate	Industrial goods	17.3	17.3
				Dimethylbenzene	Industrial goods	6	6
Methyl iso-butyl ketone (MIBK)	Industrial goods	5.5	5.5
				3-ethoxyl ethyl propionate (EthyL 3-Ethoxypropionate)	Industrial goods	3	3
S-100 solvent oil	Industrial goods	3	3
				UV light absorber THASORB UV 1130	Industrial goods	0.8	0.8
UV light absorber THASORB UV 292	Industrial goods	0.4	0.4
				The anti-shrinkage cavity flow agent of BYK-315N	Industrial goods	0.3	0.3
EFKA 360050% solution	Industrial goods	0.2	0.2
				Catalysts for polyurethanes (25% content organotin solution)	Industrial goods	0.5	0.5
Add up to		100	100

Making sheet condition:

Ground: phosphatization cold-rolled steel sheet (150mm*70mm*0.8mm) (snappiness tinplate)

Proportioning: varnish: standard cure agent=4:1 (weight ratio)

70 degree * 30 minutes, room temperature places test performance after 7 days, and result is shown in table 29.

Table 29

With the addition of the varnish that the acrylic ester polymer prepared by embodiment 2 is obtained as can be seen from Table 29, obtained coating surface gloss has obvious improvement.

Embodiment 15, comparative example 12

Acrylic ester polymer embodiment 3 prepared and other company's acrylic resin are made into car refinishing paint white finish paint according to table 30, weight (g) and component shown in table 30.

Table 30

Proportioning: finish paint: solidifying agent: thinner=100:25:35 (weight ratio)

70 degree * 30 minutes, room temperature places test performance after 7 days, and result is shown in table 31.

Table 31

As can be seen from table 31: with the addition of the white finish paint that embodiment 3 acrylic resin is obtained, obtained coating surface gloss has obvious improvement.

Acrylic ester polymer in the present invention introduces anchoring group, improves the consistency between acrylic resin and the larger resin of these two kinds of molecular structures differences of cellulose acetate butyrate greatly, also can improve the gloss of film, fullness ratio, clarity simultaneously; Designed by the technical parameter (molecular weight, second-order transition temperature, solubility parameter and hydroxyl value) of acrylic resin, obtaining a parameter area value number-average molecular weight is Mn=4500 ~ 9500, weight-average molecular weight Mw=20000 ~ 60000, molecular weight distribution is 3 ~ 8; Solubility parameter (SP value) is 10.2 ~ 10.55; Second-order transition temperature (Tg value) is 4 ~ 64 DEG C; Hydroxyl value is 40 ~ 80mgKOH/g.The acrylic resin of different performance can be designed as required, the consistency had with cellulose acetate butyrate in described value range; Can be applied in thermoplastic acrylic resin and baking-type acrylic resin further; Painting except being applied in car repair, also can be widely used in other and can use in the coating of cellulose acetate butyrate and acrylic resin; As the varnish of transparent metal varnish, Plastic, the varnish, amino-stoving varnish, vehicle paint base, metal flash paint, ultraviolet-curing paint etc. of timber.

Obviously; described embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; the basis of described explanation can also make other changes in different forms; the embodiment that the present invention exemplifies cannot give limit to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.The all documents mentioned in the present invention are quoted as a reference all in this application, as same section document is cited as separately with reference to such.

Claims (13)

1. an acrylic ester polymer, is characterized in that: have following repeated structural unit:

N=5 ~ 13, R is selected from C ₁~ C ₆alkyl.

2. acrylic ester polymer according to claim 1, it is characterized in that: the number-average molecular weight Mn of described acrylic ester polymer is 4500 ~ 9500, weight-average molecular weight Mw is 20000 ~ 60000, dispersity Mw/Mn is 3 ~ 8, glass transition temperature Tg is 4 ~ 64 DEG C, hydroxyl value is 40 ~ 80mgKOH/g, solubility parameter SP is 10.2 ~ 10.55.

3. a preparation method for the acrylic ester polymer described in claim 1 or 2, is characterized in that: comprise the following steps:

Under nitrogen protection, drip the mixture of the prepolymer MCE monomer of tertiary carbonic acid glycidyl ester and Acrylic Acid Monomer, acrylate monomer and initiator in solvent, first time insulation, adds initiator; Then second time insulation, finally adds solvent and carries out dilution adjustment solid part thus obtain described acrylic ester polymer.

4. the preparation method of acrylic ester polymer according to claim 3, is characterized in that: the consumption of described initiator is 1 ~ 3% of acrylate monomer weight;

The consumption of described MCE monomer accounts for 16 ~ 20% of MCE monomer, acrylate monomer, initiator and solvent total mass;

The consumption of described solvent accounts for 50 ~ 55% of MCE monomer, acrylate monomer, initiator and solvent total mass.

5. the preparation method of acrylic ester polymer according to claim 3, is characterized in that: the temperature of the mixture of described dropping MCE monomer, acrylate monomer and initiator is 100 ~ 115 DEG C;

3 ~ 5 hours mixture used times of described dropping MCE monomer, acrylate monomer and initiator;

The time of described first time insulation is 0.5 ~ 1 hour;

Describedly add 1.5 ~ 2.0 hours initiator used times;

The time of described second time insulation is 1.5 ~ 2.5 hours;

Described solid part is 50 ~ 55%.

6. the preparation method of acrylic ester polymer according to claim 3, is characterized in that: described acrylate monomer is at least one in vinylbenzene, ethyl propenoate, methyl acrylate, methyl methacrylate, n-butyl acrylate, isobornyl acrylate, lauryl methacrylate(LMA); Containing carboxyl functional monomer: be at least one in methacrylic acid, vinylformic acid; Hydroxy functional groups monomer: be at least one in hydroxyethyl methylacrylate, Rocryl 410, Propylene glycol monoacrylate, Hydroxyethyl acrylate.

7. the preparation method of acrylic ester polymer according to claim 3, is characterized in that: described initiator is peroxide type initiators;

Described solvent is at least one in esters solvent, benzene kind solvent.

8. the preparation method of acrylic ester polymer according to claim 7, is characterized in that: described initiator is at least one in benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methylethyl ketone peroxide, tert-butyl peroxide 2-ethylhexyl, peroxidation acetic acid tert-pentyl ester, two t-amyl peroxy compounds, peroxidation 2 ethyl hexanoic acid tert-pentyl ester;

Described esters solvent is at least one in N-BUTYL ACETATE, 1-Methoxy-2-propyl acetate;

Described benzene kind solvent is at least one in toluene, dimethylbenzene.

9. the preparation method of acrylic ester polymer according to claim 3, is characterized in that: the structural formula of described MCE monomer is as follows:

Wherein: R ₁+ R ₂carbon atom number be 7; R ₁and R ₂be selected from C ₁~ C ₆alkyl.

10. the preparation method of acrylic ester polymer according to claim 9, is characterized in that: the preparation method of described MCE monomer comprises the following steps:

Tertiary carbonic acid glycidyl ester is dissolved in solvent, carboxylic Acrylic Acid Monomer is instilled in described tertiary carbonic acid glycidyl ester solution, under the protection of stopper, the obtained described MCE monomer of reaction under high temperature.

The preparation method of 11. acrylic ester polymers according to claim 10, is characterized in that: described carboxylic Acrylic Acid Monomer is at least one in vinylformic acid, methacrylic acid;

The consumption of described carboxylic Acrylic Acid Monomer is 1 ~ 1.2 times of tertiary carbonic acid glycidyl ester equivalent;

Described stopper is phenolic inhibitor, and consumption accounts for 0.05% of carboxylic Acrylic Acid Monomer weight;

Described solvent is at least one in esters solvent, benzene kind solvent; Adjustment solid part is 70 ~ 90%;

The temperature of described reaction is 140 ~ 150 DEG C; Reaction end is judged 15 ~ 35 by controlling acid number.

The preparation method of 12. acrylic ester polymers according to claim 11, is characterized in that:

Described carboxylic Acrylic Acid Monomer is methacrylic acid;

Described stopper is at least one in Resorcinol, tert-butyl catechol, Pyrogentisinic Acid's monobutyl ether;

Described esters solvent is N-BUTYL ACETATE;

Described benzene kind solvent is at least one in toluene, dimethylbenzene.

13. 1 kinds of acrylic ester polymers prepared by the preparation method of the acrylic ester polymer described in claim 3 ~ 12 are used as the purposes of coating.