CN105237694A - Acrylate embedded copolymer as well as preparation method and application thereof - Google Patents
Acrylate embedded copolymer as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN105237694A CN105237694A CN201510791084.XA CN201510791084A CN105237694A CN 105237694 A CN105237694 A CN 105237694A CN 201510791084 A CN201510791084 A CN 201510791084A CN 105237694 A CN105237694 A CN 105237694A
- Authority
- CN
- China
- Prior art keywords
- formula
- acrylate
- alkyl
- segmented copolymer
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC(C)([C+]C(C)(C)OC(*)=O)[N+](C)(C)C=I Chemical compound CC(C)([C+]C(C)(C)OC(*)=O)[N+](C)(C)C=I 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N CN(CCC1)C1=O Chemical compound CN(CCC1)C1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- FOTOEXABUCKIFG-UHFFFAOYSA-N CC(C)(CC(C)(C)OC(C)=O)N(C)C Chemical compound CC(C)(CC(C)(C)OC(C)=O)N(C)C FOTOEXABUCKIFG-UHFFFAOYSA-N 0.000 description 1
- KYWXRBNOYGGPIZ-UHFFFAOYSA-N CC(N1CCOCC1)=O Chemical compound CC(N1CCOCC1)=O KYWXRBNOYGGPIZ-UHFFFAOYSA-N 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N CC1CCCC1 Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N CC1CCCCC1 Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N Cc1cnccc1 Chemical compound Cc1cnccc1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N Cc1ncccc1 Chemical compound Cc1ncccc1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention belongs to the field of chemical synthesis, and particularly relates to an acrylate embedded copolymer as well as a preparation method and an application thereof. The acrylate embedded copolymer comprises an embedded part of a formula (I) structure and an embedded part of formula (II) structure; a and b indicate a polymerization degree, X1 and X2 are independently selected from H or alkyl, Y1 is an alkyl or a naphthenic base, and Y2 is any one of radical groups of the formula (Y2-1) to formula (Y2-8) structures; and m1 and m2 are respectively of an integer greater than 0. By reasonably designing the structure of two embedded parts in the embedded copolymer, the dispersion performance of the embedded copolymer used as a dispersing agent can be remarkably improved. An experiment result shows that a paint film formed by a coating material with the embedded copolymer has a smooth surface and has no obvious granules; and moreover, after the coating material stands for a long time, the layering is avoided.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly relate to a kind of acrylate block copolymer and its preparation method and application.
Background technology
Dispersion agent is the interface active agent that can improve coating monodisperse system stability.Dispersion agent contains hydrophilic radical and lipophilic group in chemical structure.When it is added in coating, or hydrophilic segment or oleophilic moiety is adsorbed on pigment particle on the surface, and the non-absorbed portion of the other end just aligns outside particle surface.If particle surface is hydrophobic, then adsorbs the oleophilic moiety of dispersion agent, otherwise then adsorb hydrophilic segment.In the adsorption process of dispersion agent, the moisture on particle surface and gas etc. are substituted, and therefore, under the help of dispersion agent, the wetting action of pigment in base-material is improved, thus promote the dispersiveness of pigment in base-material.
At present, applying dispersion agent the most general is high polymer dispersion, and typical high polymer dispersion has the material of affinity to adopt the mode of block copolymerization to aggregate into living polymer respectively with pigment and base-material.Because this dispersion agent had both had the chain link of close pigment, there is again the chain link of close base-material, therefore significantly can promote the dispersiveness of pigment in base-material.
As the one of high polymer dispersion, the application of acrylic polymer dispersion agent is more and more extensive, but because the segmented structure design in existing acrylic polymer dispersion agent is unreasonable, cause the dispersing property of existing acrylic polymer dispersion agent to be difficult to meet service requirements.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of acrylate block copolymer and its preparation method and application, there is when acrylate block copolymer provided by the invention uses as dispersion agent excellent dispersing property.
The invention provides a kind of acrylate block copolymer, comprise formula (I) building block and formula (II) building block;
Wherein, a and b represents the polymerization degree, X
1and X
2independently be selected from H or alkyl, Y
1for alkyl or cycloalkyl, Y
2for having formula (Y
2-1) ~ formula (Y
2-8) any one in the group of structure:
Formula (Y
2-7) and formula (Y
2-8) in, m1 and m2 be greater than 0 integer.
Preferably, described X
1and X
2independently be selected from C
1~ C
5alkyl.
Preferably, described Y
1for C
1~ C
25alkyl or C
3~ C
25cycloalkyl.
Preferably, described Y
1for having formula (Y
1-1) ~ formula (Y
1-7) any one in the group of structure:
Formula (Y
1-1) in, 0≤n≤24.
Preferably, 0 < m1≤10,0 < m2≤10.
Preferably, 5≤a≤300; 5≤b≤100.
Preferably, any one for having in the block of formula (I-1) ~ formula (I-3) structure of described formula (I) building block:
Any one for having in the block of formula (II-1) ~ formula (II-3) structure of described formula (II) building block:
The invention provides the preparation method of the acrylate block copolymer described in a kind of technique scheme, comprise the following steps:
A), formula (III) structural compounds carries out polyreaction under chain-transfer agent and initiator exist, and obtains prepolymer;
B), described prepolymer and formula (IV) structural compounds carry out polyreaction under initiator exists, and obtains acrylate block copolymer;
Wherein, X
1and X
2independently be selected from H or alkyl, Y
1for alkyl or cycloalkyl, Y
2for having formula (Y
2-1) ~ formula (Y
2-8) any one in the group of structure:
Formula (Y
2-7) and formula (Y
2-8) in, m1 and m2 be greater than 0 integer.
The invention provides the application as dispersion agent in coating of segmented copolymer that described in segmented copolymer described in a kind of technique scheme or technique scheme, method obtains.
Preferably, described coating comprises the described segmented copolymer of the acrylic resin of 10 ~ 100 weight parts, the pigment of 10 ~ 100 weight parts and 1 ~ 10 weight part.
Compared with prior art, the invention provides a kind of acrylate block copolymer and its preparation method and application.Acrylate block copolymer provided by the invention comprises formula (I) building block and formula (II) building block; Wherein, a and b represents the polymerization degree, X
1and X
2independently be selected from H or alkyl, Y
1for alkyl or cycloalkyl, Y
2for having formula (Y
2-1) ~ formula (Y
2-8) any one in the group of structure; M1 and m2 be greater than 0 integer.The present invention by the structure of two blocks in appropriate design segmented copolymer, thus significantly improves the dispersing property of segmented copolymer when using as dispersion agent.Experimental result shows: the coating surface that the coating being added with segmented copolymer provided by the invention is formed is smooth, and without obvious particle, and this coating does not occur layering after leaving standstill for a long time.Thus prove that acrylate block copolymer provided by the invention has excellent dispersing property when using as coating dispersant, effectively can promote the dispersion of pigment in coating.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the GPC figure that the embodiment of the present invention 1 provides;
Fig. 2 is the paint film observation figure being added with the coating of vinylformic acid block copolymerization provided by the invention that the embodiment of the present invention 1 provides;
Fig. 3 is the paint film observation figure of the coating of the interpolation commercial dispersants that the embodiment of the present invention 1 provides;
Fig. 4 is the GPC figure that the embodiment of the present invention 2 provides;
Fig. 5 is the paint film observation figure being added with the coating of vinylformic acid block copolymerization provided by the invention that the embodiment of the present invention 2 provides;
Fig. 6 is the paint film observation figure of the coating of the interpolation commercial dispersants that the embodiment of the present invention 2 provides;
Fig. 7 is the GPC figure that the embodiment of the present invention 3 provides;
Fig. 8 is the coating observation figure that the embodiment of the present invention 3 provides;
Fig. 9 is that the coating that the embodiment of the present invention 3 provides leaves standstill the observation figure after 60 days.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of acrylate block copolymer, comprise formula (I) building block and formula (II) building block;
Wherein, a and b represents the polymerization degree, X
1and X
2independently be selected from H or alkyl, Y
1for alkyl or cycloalkyl, Y
2for having formula (Y
2-1) ~ formula (Y
2-8) any one in the group of structure:
Formula (Y
2-7) and formula (Y
2-8) in, m1 and m2 be greater than 0 integer.
Acrylate block copolymer provided by the invention comprises formula (I) building block and formula (II) building block.Wherein, the concrete structure of the block of formula (I) structure is as follows:
In formula (I), X
1for H or alkyl, Y
1for alkyl or cycloalkyl, a represents the polymerization degree.In an embodiment provided by the invention, X
1for C
1~ C
5alkyl; In another embodiment provided by the invention, X
1for methyl, ethyl or propyl group.In an embodiment provided by the invention, Y
1for C
1~ C
25alkyl or C
3~ C
25cycloalkyl; In another embodiment provided by the invention, Y
1for C
1~ C
22alkyl or C
3~ C
22cycloalkyl; In other embodiments provided by the invention, described Y
1for having formula (Y
1-1) ~ formula (Y
1-7) any one in the group of structure:
Formula (Y
1-1) in, 0≤n≤24.In an embodiment provided by the invention, 0≤n≤21.
In the present invention, in formula (I), a represents the polymerization degree; In an embodiment provided by the invention, 5≤a≤300; In another embodiment provided by the invention, 5≤a≤200.
In an embodiment provided by the invention, any one for having in the block of formula (I-1) ~ formula (I-3) structure of described formula (I) building block:
In the present invention, the concrete structure of the block of formula (II) structure is as follows:
In formula (II), X
2for H or alkyl, Y
2for nitrogen-containing group, b represents the polymerization degree.In an embodiment provided by the invention, X
2for C
1~ C
5alkyl; In another embodiment provided by the invention, X
2for methyl, ethyl or propyl group.In an embodiment provided by the invention, Y
2for having formula (Y
2-1) ~ formula (Y
2-8) any one in the group of structure:
Formula (Y
2-7) and formula (Y
2-8) in, m1 and m2 be greater than 0 integer.In an embodiment provided by the invention, 0 < m1≤10,0 < m2≤10; In another embodiment provided by the invention, 0 < m1≤5,0 < m2≤5; In other embodiments provided by the invention, m1=1,2 or 3, m2=1,2 or 3.
In the present invention, in formula (II), b represents the polymerization degree; In an embodiment provided by the invention, 5≤b≤100; In another embodiment provided by the invention, 5≤b≤50.
In an embodiment provided by the invention, any one for having in the block of formula (II-1) ~ formula (II-3) structure of described formula (II) building block:
In an embodiment provided by the invention, described acrylate block copolymer is made up of formula (I) building block and formula (II) building block, and its structure can represent with formula (V) general structure:
In the present invention, each substituent range of choice in formula (V) is identical with formula (II) building block with formula (I), does not repeat them here.
The present invention is by the structure of two blocks in appropriate design segmented copolymer, and significantly improve the dispersing property of segmented copolymer when using as dispersion agent, the concrete tool of acrylate block copolymer provided by the invention has the following advantages:
1), the acrylate solvent segment of acrylate block copolymer provided by the invention and formula (I) building block have very outstanding consistency, can resin compatible most of with acrylic resin, Synolac etc., thus ensure that acrylate block copolymer provided by the invention can use as dispersion agent in most cold coating, comprise furniture lacquer, industrial paint, automobile finish etc.; Particularly when described formula (I) building block is butyl polyacrylate, consistency is particularly outstanding.
2) anchoring group (nitrogen-containing group), in acrylate block copolymer provided by the invention is all in a block (formula (II) building block), therefore this segmented copolymer can combine by the pigment better and in coating, and then improves the dispersive ability of this segmented copolymer to pigment.
3), in acrylate block copolymer provided by the invention not containing the segment such as polyethers, polystyrene component, this multipolymer is structurally more simple, and clearly, therefore performance is more superior in each structural unit effect.
Experimental result shows: the coating surface that the coating being added with segmented copolymer provided by the invention is formed is smooth, without obvious particle, and there is not layering after leaving standstill for a long time in this coating, thus prove that acrylate block copolymer provided by the invention has excellent dispersing property when using as coating dispersant, effectively can promote the dispersion of pigment in coating.
The invention provides a kind of preparation method of aforesaid propylene acid esters segmented copolymer, comprise the following steps:
A), formula (III) structural compounds carries out polyreaction under chain-transfer agent and initiator exist, and obtains prepolymer;
B), described prepolymer and formula (IV) structural compounds carry out polyreaction under initiator exists, and obtains acrylate block copolymer;
Wherein, X
1and X
2independently be selected from H or alkyl, Y
1for alkyl or cycloalkyl, Y
2for having formula (Y
2-1) ~ formula (Y
2-8) any one in the group of structure:
Formula (Y
2-7) and formula (Y
2-8) in, m1 and m2 be greater than 0 integer.
In preparation method provided by the invention, first formula (III) structural compounds is carried out polyreaction.In the present invention, described formula (III) structural compounds carries out polyreaction under chain-transfer agent and initiator exist, and this process is specially:
Formula (III) structural compounds, chain-transfer agent and initiator are mixed in organic solvent, carries out polyreaction.Wherein, described formula (III) structural compounds structure is as follows:
In formula (III), X
1for H or alkyl, Y
1for alkyl or cycloalkyl.In an embodiment provided by the invention, X
1for C
1~ C
5alkyl; In another embodiment provided by the invention, X
1for methyl, ethyl or propyl group.In an embodiment provided by the invention, Y
1for C
1~ C
25alkyl or C
3~ C
25cycloalkyl; In another embodiment provided by the invention, Y
1for C
1~ C
22alkyl or C
3~ C
22cycloalkyl; In other embodiments provided by the invention, described Y
2for having formula (Y
1-1) ~ formula (Y
1-7) any one in the group of structure:
Formula (Y
1-1) in, 0≤n≤24.In an embodiment provided by the invention, 0≤n≤21.
In an embodiment provided by the invention, described formula (III) structural compounds is specially methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate acid esters, cyclohexyl acrylate, isobornyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, lauryl methacrylate(LMA), methacrylic acid 2-(ethyl hexyl) ester, stearyl methacrylate, cyclohexyl methacrylate or isobornyl methacrylate.
In the present invention, described formula (III) structural compounds, chain-transfer agent and initiator mix in the process of carrying out polyreaction in organic solvent, described chain-transfer agent include but not limited to have in the chain-transfer agent of formula (K-1) ~ formula (K-14) structure one or more:
In the present invention, described formula (III) structural compounds, chain-transfer agent and initiator mix in the process of carrying out polyreaction in organic solvent, described initiator includes but not limited to Diisopropyl azodicarboxylate, azo two isobutyl heptonitrile, benzoyl peroxide, benzoyl peroxide, peroxidation 2-ethyl acid tert-pentyl ester, the peroxidation 2-ethyl acid tert-butyl ester, 1, two (t-amyl peroxy) cyclic group alkane of 1-, 1, two (t-amyl peroxy)-3 of 1-, 3, 5-trimethylammonium cyclohexane, peroxidation acetic acid tert-pentyl ester, peroxide acid tert-amyl acetate, peroxidation 3, 5, 5 trimethylammoniums tert-butyl acrylate, peroxidized t-butyl perbenzoate, 3, two (t-amyl peroxy) ethyl butyrate of 3-, 3, two (t-butyl peroxy) ethyl butyrate of 3-, dicumyl peroxide, di t-amyl peroxide, di-t-butyl peroxide, one or more of t-amyl peroxy hydrogen and tertbutyl peroxide.
In the present invention, described formula (III) structural compounds, chain-transfer agent and initiator mix in the process of carrying out polyreaction in organic solvent, and described organic solvent includes but not limited to toluene, dimethylbenzene, ethyl acetate, butanone, isopropyl acetate, 2 pentanone, propyl acetate, hexone, isobutyl acetate, n-butyl acetate, methyl isoamyl ketone, acetic acid dissident ester, n-butyl propionate, 1-Methoxy-2-propyl acetate, pentyl acetate, methyl-n-amyl ketone, isobutyl isobutyrate, ethylene glycol ethyl ether, pimelinketone, glycol monobutyl ether, Propylene glycol n-propyl ether, 1-Methoxy-2-propyl acetate, ethyl cellosolve acetate, valerone, diacetone alcohol, butyl glycol ether, propandiol butyl ether, 2-ethyl hexyl ethanoate, butyl glycol ether acetic ester, dipropylene glycol methyl ether, glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ether, glycol hexyl ether, diethylene glycol ether acetic ester, butyl, ethylene glycol-2-ethyl hexyl ether, one kind of multiple in butyl acetic ester and propylene glycol phenylate.
In the present invention, described formula (III) structural compounds, chain-transfer agent and initiator mix in the process of carrying out polyreaction in organic solvent, the mol ratio of described formula (III) structural compounds, chain-transfer agent, initiator and organic solvent is preferably (5 ~ 300): 1:(0.1 ~ 0.5): (10 ~ 1000), are more preferably (5 ~ 200): 1:(0.1 ~ 0.5): (10 ~ 1000).Formula (III) structural compounds preferably first mixes with chain-transfer agent by the mode that described formula (III) structural compounds, chain-transfer agent and initiator mix in organic solvent, will be added drop-wise to containing the organic solvent of initiator in mixed system that formula (III) binding compounds and chain-transfer agent form afterwards again.In the present invention, the temperature of described polyreaction is preferably 50 ~ 160 DEG C.The present invention is not particularly limited the time to described polyreaction, preferably stopped reaction after the transformation efficiency of formula (III) structural compounds reaches more than 80%.In an embodiment provided by the invention, the time of described polyreaction is 6 ~ 7.5h.
In the present invention, formula (III) structural compounds carries out after polyreaction terminates, obtaining prepolymer.After obtaining described prepolymer, described prepolymer and formula (IV) structural compounds carry out polyreaction.In the present invention, described prepolymer and formula (IV) structural compounds carry out polyreaction under initiator exists, and this process is specially:
Described prepolymer, formula (IV) structural compounds and initiator are mixed in organic solvent, carries out polyreaction.Wherein, described formula (IV) structural compounds structure is as follows:
In formula (IV), X
2for H or alkyl, Y
2for nitrogen-containing group.In an embodiment provided by the invention, X
2for C
1~ C
5alkyl; In another embodiment provided by the invention, X
2for methyl, ethyl or propyl group.In an embodiment provided by the invention, Y
2for having formula (Y
2-1) ~ formula (Y
2-8) any one in the group of structure:
Formula (Y
2-7) and formula (Y
2-8) in, m1 and m2 be greater than 0 integer.In an embodiment provided by the invention, 0 < m1≤10,0 < m2≤10; In another embodiment provided by the invention, 0 < m1≤5,0 < m2≤5; In other embodiments provided by the invention, m1=1,2 or 3, m2=1,2 or 3.
In an embodiment provided by the invention, described formula (IV) structural compounds is specially N, N-dimethyl amino ethyl acrylate, 2-trimethylethyl vinylformic acid ammonium chloride, N, N-dimethylaminopropylacryl acid esters, 4-vinylpridine, 2-vinyl pyridine, vinyl imidazole, N-caprolactam, NVP, 4-acryloyl morpholine, N, N-dimethyl amino ethyl methacrylate, 2-trimethylethyl methacrylic acid ammonium chloride or N, N-dimethylaminopropyl methacrylic ester.
In the present invention, described prepolymer, formula (IV) structural compounds and initiator mix in the process of carrying out polyreaction in organic solvent, described initiator includes but not limited to Diisopropyl azodicarboxylate, azo two isobutyl heptonitrile, benzoyl peroxide, benzoyl peroxide, peroxidation 2-ethyl acid tert-pentyl ester, the peroxidation 2-ethyl acid tert-butyl ester, 1, two (t-amyl peroxy) cyclic group alkane of 1-, 1, two (t-amyl peroxy)-3 of 1-, 3, 5-trimethylammonium cyclohexane, peroxidation acetic acid tert-pentyl ester, peroxide acid tert-amyl acetate, peroxidation 3, 5, 5 trimethylammoniums tert-butyl acrylate, peroxidized t-butyl perbenzoate, 3, two (t-amyl peroxy) ethyl butyrate of 3-, 3, two (t-butyl peroxy) ethyl butyrate of 3-, dicumyl peroxide, di t-amyl peroxide, di-t-butyl peroxide, one or more of t-amyl peroxy hydrogen and tertbutyl peroxide.
In the present invention, described prepolymer, formula (IV) structural compounds and initiator mix in the process of carrying out polyreaction in organic solvent, and described organic solvent includes but not limited to toluene, dimethylbenzene, ethyl acetate, butanone, isopropyl acetate, 2 pentanone, propyl acetate, hexone, isobutyl acetate, n-butyl acetate, methyl isoamyl ketone, acetic acid dissident ester, n-butyl propionate, 1-Methoxy-2-propyl acetate, pentyl acetate, methyl-n-amyl ketone, isobutyl isobutyrate, ethylene glycol ethyl ether, pimelinketone, glycol monobutyl ether, Propylene glycol n-propyl ether, 1-Methoxy-2-propyl acetate, ethyl cellosolve acetate, valerone, diacetone alcohol, butyl glycol ether, propandiol butyl ether, 2-ethyl hexyl ethanoate, butyl glycol ether acetic ester, dipropylene glycol methyl ether, glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ether, glycol hexyl ether, diethylene glycol ether acetic ester, butyl, ethylene glycol-2-ethyl hexyl ether, one kind of multiple in butyl acetic ester and propylene glycol phenylate.
In the present invention, described prepolymer, formula (IV) structural compounds and initiator mix in the process of carrying out polyreaction in organic solvent, the mol ratio of the raw material and formula (III) structural compounds, formula (IV) structural compounds, initiator and organic solvent of preparing described prepolymer is preferably (5 ~ 300): (5 ~ 100): (0.1 ~ 0.5): (10 ~ 1000), are more preferably (5 ~ 200): (5 ~ 50): (0.1 ~ 0.5): (10 ~ 1000).The mode that described prepolymer, formula (IV) structural compounds and initiator mix in organic solvent is preferably first by described prepolymer and the mixing of formula (IV) structural compounds, is added drop-wise to by the organic solvent containing initiator more afterwards in the mixed system of prepolymer and formula (IV) structural compounds composition.In the present invention, the temperature of described polyreaction is preferably 50 ~ 160 DEG C.The present invention is not particularly limited the time to described polyreaction, preferably stopped reaction after the transformation efficiency of formula (IV) structural compounds reaches 100%.In an embodiment provided by the invention, the time of described polyreaction is 7 ~ 8h.
In the present invention, prepolymer and formula (IV) structural compounds carry out after polyreaction terminates, obtaining acrylate block copolymer provided by the invention.
Method provided by the invention with formula (III) structural compounds and formula (IV) structural compounds for comonomer, adopt the mode of step-by-step polymerization to prepare acrylate block copolymer, this segmented copolymer uses the excellent dispersion performance shown as dispersion agent.The concrete tool of preparation method provided by the invention has the following advantages:
1), preparation method provided by the invention for environmental requirement milder, more tolerant to reaction unit, monomer selects face wider, and adaptability is stronger; Meanwhile, the block polymer molecules amount adopting method provided by the invention to prepare is controlled, and molecular weight distribution is narrower.
2), in preferred implementation provided by the invention, adopt the chain-transfer agent with formula (K-1) ~ formula (K-14) structure, this transfer agent preparation process is simple, is applicable to industrializing implementation.
Experimental result shows: the coating surface that the coating being added with the segmented copolymer that the method for the invention provides obtains is formed is smooth, without obvious particle, and there is not layering after leaving standstill for a long time in this coating, thus prove that the acrylate block copolymer that the method that the invention provides obtains has excellent dispersing property when using as coating dispersant, effectively can promote the dispersion of pigment in coating.
A kind of segmented copolymer method described in segmented copolymer described in technique scheme or technique scheme obtained provided by the invention is as the application of dispersion agent in coating.
In application provided by the invention, use as coating dispersant using described segmented copolymer, add to after in coating and show excellent dispersing property.In an embodiment provided by the invention, described coating comprises the described segmented copolymer of the acrylic resin of 10 ~ 100 weight parts, the pigment of 10 ~ 100 weight parts and 1 ~ 10 weight part; In another embodiment provided by the invention, described coating comprises the described segmented copolymer of the acrylic resin of 10 ~ 60 weight parts, the pigment of 10 ~ 60 weight parts and 1 ~ 7 weight part.In the present invention, described pigment includes but not limited to one or more in titanium dioxide, carbon black and phthalocyanine blue.In an embodiment provided by the invention, described coating also comprises solvent, and described solvent is preferably dimethylbenzene (enumerating other solvents), and the addition of described solvent in coating is preferably 2 ~ 60 weight parts.
For the purpose of clearer, be described in detail below by following examples.
Embodiment 1
1), acrylate block copolymer is prepared:
1-1), the preparation of prepolymer:
Chain-transfer agent, the 5mol methyl acrylate 1mol with formula (K-1) structure join in reactor, pass into nitrogen 10min, the xylene solution (mol ratio of Diisopropyl azodicarboxylate and dimethylbenzene is 0.1:10) containing 0.1mol Diisopropyl azodicarboxylate is slowly dripped at temperature is 50 DEG C, after dripping the xylene solution containing Diisopropyl azodicarboxylate, methyl acrylate starts to carry out polyreaction, after question response 6h, stopped reaction, obtains prepolymer.
Gas-chromatography is adopted to detect the content of methyl acrylate in described prepolymer, and the transformation efficiency of cubage methyl acrylate according to methyl acrylate, result is: the transformation efficiency of methyl acrylate reaches 80%.
1-2), the preparation of block polymer:
The prepolymer of preparation is joined in reactor, and add N, N-dimethyl amino ethyl acrylate 5mol, the xylene solution (mol ratio of benzoyl peroxide and dimethylbenzene is 0.1:10) containing 0.1mol benzoyl peroxide is slowly dripped at temperature is 50 DEG C, after dripping the xylene solution containing benzoyl peroxide, prepolymer and N, N-dimethyl amino ethyl acrylate starts to carry out polyreaction, after question response 7.5h, stopped reaction, obtains acrylate block copolymer.
Adopt gas-chromatography to N in described acrylate block copolymer, the content of N-dimethyl amino ethyl acrylate detects, and according to N, the cubage N of N-dimethyl amino ethyl acrylate, the transformation efficiency of N-dimethyl amino ethyl acrylate, result is: the transformation efficiency of N, N-dimethyl amino ethyl acrylate reaches 100%.
Gel permeation chromatography (GelPermeationChromatography is carried out to obtained acrylate block copolymer, GPC) analyze, result as shown in Figure 1, Fig. 1 is the GPC figure that the embodiment of the present invention 1 provides, as seen in Figure 1, the number-average molecular weight of this acrylate block copolymer is 1620g/mol, and molecular weight distribution index (PDI) is 1.21.
The segmented copolymer that the obtained acrylate block copolymer of the present embodiment is formula (I-1) building block and formula (II-1) building block composition can be extrapolated according to raw material type, raw material feed ratio and gpc analysis result:
Wherein, a=5, b=5.
2), the application of acrylate block copolymer in coating of preparation:
By 35 grams of acrylic resins (producer: fine horse nation, model: 32221), 60 grams of titanium dioxides, 1 gram of above-mentioned obtained acrylate block copolymer join in dispersion cylinder together with 4 grams of dimethylbenzene, stir 20min at 1200rpm/min, obtain whitewash 1.
By 35 grams of acrylic resins, (producer: fine horse nation, model: 32221), 60 grams of titanium dioxides, 1 gram of certain commercial dispersants join in dispersion cylinder together with 4 grams of dimethylbenzene, stirs 20min at 1200rpm/min, obtains whitewash 2.
The film on tinplate by above-mentioned whitewash 1 and whitewash 2, observe paint film, as shown in Figures 2 and 3, Fig. 2 is the paint film observation figure being added with the coating of vinylformic acid block copolymerization provided by the invention that the embodiment of the present invention 1 provides to paint film observations; Fig. 3 is the paint film observation figure of the coating of the interpolation commercial dispersants that the embodiment of the present invention 1 provides.Relatively can find out by Fig. 2 and Fig. 3, the coating surface in Fig. 2 is smooth, and without obvious particle, the paint film in Fig. 3 has obvious particle.Thus prove that the acrylate block copolymer that the present embodiment provides has excellent dispersing property when using as coating dispersant, effectively can promote the dispersion of pigment in cold coating.
Embodiment 2
1), acrylate block copolymer is prepared:
1-1), the preparation of solvation segment:
1mol had the chain-transfer agent of formula (K-5) structure, 100mol stearyl acrylate acid esters joins in reactor, pass into nitrogen 30min, the ethyl cellosolve acetate solution (mol ratio of the peroxidation 2-ethyl acid tert-butyl ester and ethyl cellosolve acetate is 0.3:500) containing the 0.3mol peroxidation 2-ethyl acid tert-butyl ester is slowly dripped at temperature is 100 DEG C, after dripping the ethyl cellosolve acetate solution containing the peroxidation 2-ethyl acid tert-butyl ester, stearyl acrylate acid esters starts to carry out polyreaction, after question response 6.5h, stopped reaction, obtain prepolymer.
Gas-chromatography is adopted to detect the amount of stearyl acrylate acid esters in described prepolymer, and the transformation efficiency of cubage stearyl acrylate acid esters according to stearyl acrylate acid esters, result is: the transformation efficiency of stearyl acrylate acid esters reaches 90%.
1-2), the preparation of block polymer:
The prepolymer of preparation is joined in reactor, and add 2-trimethylethyl vinylformic acid ammonium chloride 20mol, the ethyl cellosolve acetate solution (mol ratio of the peroxidation 2-ethyl acid tert-butyl ester and ethyl cellosolve acetate is 0.3:500) containing the 0.3mol peroxidation 2-ethyl acid tert-butyl ester is also slowly dripped at temperature is 100 DEG C, after dripping the ethyl cellosolve acetate solution containing the peroxidation 2-ethyl acid tert-butyl ester, prepolymer and 2-trimethylethyl vinylformic acid ammonium chloride start to carry out polyreaction, after question response 7.5h, stopped reaction, obtain acrylate block copolymer.
Gas-chromatography is adopted to detect the content of 2-trimethylethyl vinylformic acid ammonium chloride in described acrylate block copolymer, and the transformation efficiency of cubage 2-trimethylethyl vinylformic acid ammonium chloride according to 2-trimethylethyl vinylformic acid ammonium chloride, result is: the transformation efficiency of 2-trimethylethyl vinylformic acid ammonium chloride reaches 100%.
Gel permeation chromatography (GelPermeationChromatography is carried out to obtained acrylate block copolymer, GPC) analyze, result as shown in Figure 4, Fig. 4 is the GPC figure that the embodiment of the present invention 2 provides, as seen in Figure 4, the number-average molecular weight of this acrylate block copolymer is 38000g/mol, and molecular weight distribution index (PDI) is 1.29.
The segmented copolymer that the obtained acrylate block copolymer of the present embodiment is formula (I-2) building block and formula (II-2) building block composition can be extrapolated according to raw material type, raw material feed ratio and gpc analysis result:
Wherein, a=100, b=20.
2), the application of acrylate block copolymer in coating of preparation:
By 60 grams of acrylic resins (producer: fine horse nation, model: 32221), 10 grams of high-carbon black pigment FW200,3 grams of above-mentioned obtained acrylate block copolymers, 15 grams of transparent powders and 12 grams of dimethylbenzene one reinstate three-roll grinder grinding, obtain blackwash 1.
By 60 grams of acrylic resins (producer: fine horse nation, model: 32221), 10 grams of high-carbon black pigment FW200,3 grams of certain commercial dispersants, 15 grams of transparent powders and 12 grams of dimethylbenzene one reinstate three-roll grinder grinding, obtain blackwash 2.
The film on timber by above-mentioned aluminum-bronze paint 1 and aluminum-bronze paint 2, observe paint film, as shown in Figure 5 and Figure 6, Fig. 5 is the paint film observation figure being added with the coating of vinylformic acid block copolymerization provided by the invention that the embodiment of the present invention 2 provides to paint film observations; Fig. 6 is the paint film observation figure of the coating of the interpolation commercial dispersants that the embodiment of the present invention 2 provides.Relatively can find out by Fig. 5 and Fig. 6, the coating surface in Fig. 5 is smooth.Without obvious particle, the paint film in Fig. 6 has obvious particle.Thus prove that the acrylate block copolymer that the present embodiment provides has excellent dispersing property when using as coating dispersant, effectively can promote the dispersion of pigment in cold coating.
Embodiment 3
1), acrylate block copolymer is prepared:
1-1), the preparation of solvation segment:
Chain-transfer agent, the 200mol isobornyl acrylate 1mol with formula (K-14) structure join in reactor, pass into nitrogen 60min, the acetic acid dissident ester solution (mol ratio of peroxide acid tert-amyl acetate and acetic acid dissident ester is 0.5:1000) containing 0.5mol peroxide acid tert-amyl acetate is slowly dripped at temperature is 160 DEG C, after dripping the acetic acid dissident ester solution containing peroxide acid tert-amyl acetate, isobornyl acrylate starts to carry out polyreaction, after question response 7.5h, stopped reaction, obtains prepolymer.
Gas-chromatography is adopted to detect the content of isobornyl acrylate in described prepolymer, and the transformation efficiency of cubage isobornyl acrylate according to isobornyl acrylate, result is: the transformation efficiency of isobornyl acrylate reaches 100%.
1-2), the preparation of block polymer:
The prepolymer of preparation is joined in reactor, and add NVP 50mol, and the acetic acid dissident ester solution (mol ratio of peroxide acid tert-amyl acetate and acetic acid dissident ester is 0.5:1000) slowly dripped containing 0.5mol peroxide acid tert-amyl acetate, after dripping the acetic acid dissident ester solution containing peroxide acid tert-amyl acetate, prepolymer and NVP start to carry out polyreaction, after question response 7.5h, stopped reaction, obtains acrylate block copolymer.
Gas-chromatography is adopted to detect the content of NVP in described acrylate block copolymer, and the transformation efficiency of cubage NVP according to NVP, result is: the transformation efficiency of NVP reaches 100%.
Gel permeation chromatography (GelPermeationChromatography is carried out to obtained acrylate block copolymer, GPC) analyze, result as shown in Figure 7, Fig. 7 is the GPC figure that the embodiment of the present invention 3 provides, as seen in Figure 7, the number-average molecular weight of this acrylate block copolymer is 50000g/mol, and molecular weight distribution index (PDI) is 1.33.
The segmented copolymer that the obtained acrylate block copolymer of the present embodiment is formula (I-3) building block and formula (II-3) building block composition can be extrapolated according to raw material type, raw material feed ratio and gpc analysis result:
Wherein, a=200, b=50.
2), the application of acrylate block copolymer in coating of preparation:
By 10 grams of acrylic resins (producer: fine horse nation, model: 32221), 30 grams of phthalocyanine blues, 7 grams of above-mentioned obtained acrylate block copolymers and 53 grams of dimethylbenzene one reinstates three-roll grinder to be ground to fineness qualified, obtains blue paste 1.
By 10 grams of acrylic resins (producer: fine horse nation, model: 32221), 30 grams of phthalocyanine blues, 7 grams of certain commercial dispersants and 53 grams of dimethylbenzene one reinstates three-roll grinder to be ground to fineness qualified, obtains blue paste 2.
Observe obtained blue paste 1 and blue paste 2, as shown in Figure 8 and Figure 9, Fig. 8 is the coating observation figure that the embodiment of the present invention 3 provides to result, and wherein, label B1's is blue paste 1, and label B2's is blue paste 2; Fig. 9 is that the coating that the embodiment of the present invention 3 provides leaves standstill the observation figure after 60 days, and wherein, label B1's is blue paste 1, and label B2's is blue paste 2.
As seen in Figure 8, the acrylate block copolymer that provides of the present embodiment and commercial dispersants all have good dispersiveness to phthalocyanine blue.As seen in Figure 9, compared to the acrylate block copolymer that the present embodiment provides, the dispersion stabilization of commercial dispersants to phthalocyanine blue is poor, coating leaves standstill and occurs demixing phenomenon after 60 days, and the acrylate block copolymer that the present embodiment provides is very stable to the dispersiveness of phthalocyanine blue, there is not layering.Thus prove that the acrylate block copolymer that the present embodiment provides has excellent dispersing property when using as coating dispersant, effectively can promote the dispersion of pigment in cold coating.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. an acrylate block copolymer, comprises formula (I) building block and formula (II) building block;
Wherein, a and b represents the polymerization degree, X
1and X
2independently be selected from H or alkyl, Y
1for alkyl or cycloalkyl, Y
2for having formula (Y
2-1) ~ formula (Y
2-8) any one in the group of structure:
Formula (Y
2-7) and formula (Y
2-8) in, m1 and m2 be greater than 0 integer.
2. segmented copolymer according to claim 1, is characterized in that, described X
1and X
2independently be selected from C
1~ C
5alkyl.
3. segmented copolymer according to claim 1, is characterized in that, described Y
1for C
1~ C
25alkyl or C
3~ C
25cycloalkyl.
4. segmented copolymer according to claim 3, is characterized in that, described Y
1for having formula (Y
1-1) ~ formula (Y
1-7) any one in the group of structure:
Formula (Y
1-1) in, 0≤n≤24.
5. segmented copolymer according to claim 1, is characterized in that, 0 < m1≤10,0 < m2≤10.
6. segmented copolymer according to claim 1, is characterized in that, 5≤a≤300; 5≤b≤100.
7. segmented copolymer according to claim 1, is characterized in that, any one for having in the block of formula (I-1) ~ formula (I-3) structure of described formula (I) building block:
Any one for having in the block of formula (II-1) ~ formula (II-3) structure of described formula (II) building block:
8. a preparation method for acrylate block copolymer according to claim 1, comprises the following steps:
A), formula (III) structural compounds carries out polyreaction under chain-transfer agent and initiator exist, and obtains prepolymer;
B), described prepolymer and formula (IV) structural compounds carry out polyreaction under initiator exists, and obtains acrylate block copolymer;
Wherein, X
1and X
2independently be selected from H or alkyl, Y
1for alkyl or cycloalkyl, Y
2for having formula (Y
2-1) ~ formula (Y
2-8) any one in the group of structure:
Formula (Y
2-7) and formula (Y
2-8) in, m1 and m2 be greater than 0 integer.
9. the segmented copolymer that described in the segmented copolymer described in an any one of claim 1 ~ 7 or claim 8, method obtains is as the application of dispersion agent in coating.
10. application according to claim 9, is characterized in that, described coating comprises the described segmented copolymer of the acrylic resin of 10 ~ 100 weight parts, the pigment of 10 ~ 100 weight parts and 1 ~ 10 weight part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510791084.XA CN105237694B (en) | 2015-11-17 | 2015-11-17 | A kind of acrylate block copolymer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510791084.XA CN105237694B (en) | 2015-11-17 | 2015-11-17 | A kind of acrylate block copolymer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105237694A true CN105237694A (en) | 2016-01-13 |
| CN105237694B CN105237694B (en) | 2018-06-29 |
Family
ID=55035553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510791084.XA Active CN105237694B (en) | 2015-11-17 | 2015-11-17 | A kind of acrylate block copolymer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105237694B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286276A (en) * | 1999-08-28 | 2001-03-07 | 比克化学股份有限公司 | Branched polymer contg. imidazolyl, producing method and use thereof |
| CN1386794A (en) * | 2001-05-21 | 2002-12-25 | 西巴特殊化学品控股有限公司 | Pigment compositions with modified block copolymer dispersants |
| CN1735636A (en) * | 2002-11-07 | 2006-02-15 | 罗地亚化学公司 | Controlled structure copolymer comprising an amphoteric or zwitterionic part |
| CN103497272A (en) * | 2013-09-29 | 2014-01-08 | 华南理工大学 | Polymer emulsion and preparation method thereof |
-
2015
- 2015-11-17 CN CN201510791084.XA patent/CN105237694B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286276A (en) * | 1999-08-28 | 2001-03-07 | 比克化学股份有限公司 | Branched polymer contg. imidazolyl, producing method and use thereof |
| CN1386794A (en) * | 2001-05-21 | 2002-12-25 | 西巴特殊化学品控股有限公司 | Pigment compositions with modified block copolymer dispersants |
| CN1735636A (en) * | 2002-11-07 | 2006-02-15 | 罗地亚化学公司 | Controlled structure copolymer comprising an amphoteric or zwitterionic part |
| CN103497272A (en) * | 2013-09-29 | 2014-01-08 | 华南理工大学 | Polymer emulsion and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 徐峰: "《建筑涂料》", 31 August 2007 * |
| 杨春晖: "《涂料配方设计与制备工艺》", 31 May 2003 * |
| 汪长春: "《丙烯酸酯涂料》", 30 April 2005 * |
| 熊清凤: "RAFT活性自由基聚合合成嵌段聚合物", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 肖成贵: "N-乙烯基吡咯烷酮的反向原子转移自由基聚合", 《高分子材料科学与工程》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105237694B (en) | 2018-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103482897B (en) | A kind of block polycarboxylic acid concrete high efficiency water reducing agent and preparation method thereof | |
| US20040143035A1 (en) | Use of gradient copolymers as dispersants to treat pigments and other solids | |
| CN106554446B (en) | A kind of fast preparation method of multifunctionality fluoropolymer microballoon | |
| CN102532436B (en) | Method for preparing single-component room-temperature crosslinked waterborne fluorine-containing coating | |
| CN102993387A (en) | Method for directly synthesizing pure solid high-performance polycarboxylate water-reducer in one step | |
| CN101921373A (en) | A kind of acrylic modified epoxy resin emulsion and preparation method thereof | |
| CN104231148A (en) | Hydroxyl acrylic resin and preparation method thereof | |
| CN103012714A (en) | High-flexibility aqueous acrylic acid polyurethane elastic resin and coating thereof | |
| CN102039100A (en) | Amphipathic graft polymer pigment dispersing agent and synthesis process thereof | |
| CN115975104A (en) | A kind of acrylate comb dispersant and preparation method | |
| CN106467603B (en) | A kind of anionic dispersing agents and its preparation method and application | |
| CN105732909B (en) | A kind of preparation method of acrylic polysiloxane water-based emulsion | |
| JP6048913B2 (en) | Water-soluble polymer pigment dispersant and water-based composition containing water-soluble polymer pigment dispersant | |
| CN105837757B (en) | Microgel aqueous acrylic acid shell-core resin emulsion and preparation method thereof | |
| CN105713132A (en) | High-hardness water-borne wood paint and preparation method thereof | |
| CN110982003B (en) | Preparation method of star polymer dispersant, product and application thereof | |
| CN102492100B (en) | Water-dispersed fluorine-containing hydroxyl acrylic-epoxy ester heterozygous body resin and coating thereof | |
| CN103031011A (en) | Laser transfer paint suitable for intaglio printing and preparation method of same | |
| CN112266438A (en) | Methyl methacrylate polymer and preparation method and application thereof | |
| CN105237694A (en) | Acrylate embedded copolymer as well as preparation method and application thereof | |
| CN109054533B (en) | A kind of polymer coating and preparation method thereof | |
| CN111285953B (en) | Acrylic emulsion and preparation method thereof | |
| CN119143941A (en) | Acrylic ester hyperdispersant for preventing paint from flooding and preparation method thereof | |
| CN106397656B (en) | A kind of preparation and application of water-based hydrophobic modified polymethyl hydrochlorate dispersant | |
| CN103408698A (en) | In-situ redox initiation for preparing polyacrylamide water-drum water dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |