CN108084355A - Acrylate containing dissaving structure and preparation method thereof - Google Patents
Acrylate containing dissaving structure and preparation method thereof Download PDFInfo
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- CN108084355A CN108084355A CN201711366265.3A CN201711366265A CN108084355A CN 108084355 A CN108084355 A CN 108084355A CN 201711366265 A CN201711366265 A CN 201711366265A CN 108084355 A CN108084355 A CN 108084355A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
- C08F283/045—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides on to unsaturated polycarbonamides, polyesteramides or polyimides
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/32—Modified amine-aldehyde condensates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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Abstract
The invention discloses a kind of acrylates containing dissaving structure and preparation method thereof, using progressively development method synthesized two kinds of inside with outside double bond with hydroxyl, carboxyl isoreactivity functional group hyperbranched polymeric monomer --- polyester-type and the hyperbranched polymeric monomer of poly- (ester-acid amide) type characterize hyperbranched polymeric monomer and its building-up process by the methods of infrared, GPC, acid value and hydroxy value measuring.The synthesized hyperbranched polymeric monomer of two classes is applied to the synthesis of acrylic resin, it has prepared with superelevation degree of branching structure, the acrylate compared with low viscosity, the resin is available for preparation high solid self-drying paint, high solid baked paint, high solid two-component air-curing coatings and adhesive is used as to use.The present invention can effectively reduce the organic solvent content of acrylate in the production and use process, reduce the pollution to environment, and function admirable.
Description
Technical field
Preparation, hyperbranched type polymeric monomer and acrylic ester monomer the present invention relates to the polymeric monomer of type containing vinyl ultra-branching
Application in high solid coating and adhesive of copolymerization and its copolymerization product.
Background technology
In coating and adhesives industry, acrylate is because with many excellent characteristic (such as weatherabilities, light transmission
Property, flexibility, chemical stability etc.) and be widely used.Traditional acrylate is through even using vinyl monomer
The linear polymer that lock polymerization obtains, thus intermolecular entanglement is serious at higher concentrations, has the larger resistance of motion,
Higher kinematic viscosity is shown as, so as to which directly use brings difficulty to it.In addition, some active functions in molecular structure
Group causes reactivity to reduce by being coated by long-chain due to steric hindrance reason.So acrylate made from conventional method
The shortcomings that resin is active low there is viscosity height.Therefore, manufacturer and usually being needed using unit adds in a large amount of wherein
Organic solvent, to reduce the viscosity of acrylate in the production and use process, these organic solvents are in drying process
In can evaporate into air.Therefore substantial amounts of non-renewable resources are not only wasted, and serious pollution is caused to environment.
The Chinese Central Television (CCTV) once reported that the number that China directly dies of organic pollution every year was 110,000 people；Pathogenic number is up to more than 300 ten thousand；
Direct economic loss is 10,000,000,000 dollars or more.Therefore need to find new approach reduction resin viscosity in a hurry, to be greatly lowered
The usage amount of organic solvent, the living environment for protecting the mankind.
Since dissaving polymer has smaller hydrodynamic volume, thus viscosity is relatively low in the solution.Preparation has
The acrylate of dissaving structure, it will the viscosity of system is substantially reduced, so as to which the use of organic solvent be greatly lowered
Amount reduces pollution of the organic solvent to environment, saves non-renewable resources.
The polymer of current dissaving structure, mostly by alcohol, acid, amine of small molecule of not vinyl-containing monomers etc., according to by
The polycondensation reaction of step polymerization is prepared, but needed for its molecular weight is extremely difficult to, thus application is subject to certain restrictions.And by second
Alkenyl class monomer (acrylic acid, acrylate etc.) prepares the polymerisation of acrylate and polymerize for radical chain, can be with
The product of higher molecular weight is obtained, but its structure is straight chain type, hardly results in dissaving structure, its application is caused to be similarly subjected to
Limitation.External useful free radical polymerization obtains the report of branched structure polymer, and the method used is added in reaction monomers
Enter with crosslinked action bi-vinyl class monomer, but this method is easy to generate gel.The generation of gel in order to prevent, usually
It needs to add in substantial amounts of, expensive chain-transferring agent in the reaction system.Also have using RAFT (Reversible
Addition-Fragmentation Chain Transfer Polymerization) polymerization, i.e., in RAFT reagents
In the presence of, the polymerisation of progress.In the existing Raolical polymerizable for having RAFT reagents, because higher ratio can be added in
The bi-vinyl class monomer of example, so as to improve the degree of branching of polymerizate.But the drawback is that reaction time it is too long, cost
It is high.
Therefore, it is badly in need of design and prepares in addition to the required vinyl of free radical polymerization can be carried out, also with branched
The polymeric monomer of structure, while ensure that later stage polymerization is easy, cheap, molecular weight can reach high solid coating and adhesive will
The acrylate asked.
Wherein, hydroxyl value and the measuring method of acid value are as follows：
First, the measurement of hydroxyl value
A certain amount of sample w (g) is accurately weighed, is dissolved in acetic anhydride/pyridine (v/v=1:5) in mixed solution, in reflux temperature
Degree is lower to keep 1.5h, makes its acetylation, 20ml water is added in after cooling, titrated, measured with the KOH- ethanol solutions of 0.5mo l/L
Polymer hydroxyl value.
M, V are the sample quality g weighed for KOH substance withdrawl syndrome mo l/L and consumption volume L, W in formula.
2nd, the measure of acid value
W (g) samples accurately are weighed, are dissolved in dimethylbenzene/ethyl alcohol (v/v=3:2) in mixed solution, dissolving, with 0.2mo l/
LKOH solution titrates, and calculates polymer acid number.
M, V are the sample quality g weighed for KOH substance withdrawl syndrome mo l/L and consumption volume L, W in formula.
The content of the invention
The technical problems to be solved by the invention are：In order to overcome the above-mentioned problems in the prior art, one is now provided
The preparation method of the preparation method of the hyperbranched polymeric monomer of kind and the acrylate containing dissaving structure.
The present invention solves its technical problem technical solution to be taken：A kind of hyperbranched polymeric monomer, it is described hyperbranched
Polymeric monomer has the branched structure of three or more, and at least contains vinyl on a branch, the hyperbranched polymeric monomer edge
Strand has multiple hydroxyls or carboxyl distribution, under free radical initiation, can be polymerize with acrylic monomer or graft reaction,
And curing crosslinking can be carried out under certain condition with amino, isocyanate group etc..
The hyperbranched polymeric monomer can be following two types：One kind is polyester type hyperbranched polymeric monomer；One kind is
The hyperbranched polymeric monomer of polyamide.
The preparation method of hyperbranched polymeric monomer provided by the invention is the method by using fed batch, anti-through multistep
It should obtain, comprise the following steps：
A. double bond, A monomer of functional group's number more than or equal to 2 and B monomer reaction of the functional group more than or equal to 2 will be contained,
Obtain molecular weight bigger and the C performed polymers containing double bond；
B.C performed polymers and B monomer further carry out polycondensation reaction, are increased the degree of branching of molecule, through multistep polycondensation,
Hyperbranched polymeric monomer is finally obtained, the hyperbranched polymeric monomer contains ethylene that can further with other vinyl monomer combined polymerizations
Based structures, end remain with multiple unreacted functional groups, can be used in last cross-linking reaction as active crosslinking points.
The A monomers are：Contain double bond, maleic acid of functional group's number more than or equal to 2, maleic anhydride；
The B monomer is：N,N-dimethylformamide of functional group's number more than or equal to 2, diethanol amine, maleic two
Acid, glycerine, pentaerythrite, trimethylolpropane, phthalic acid, phthalic anhydride, maleic anhydride, trimellitic acid
One or more of mixtures of acid anhydride etc.；
The organic acid of the simple functions such as stearic acid, lauric acid, cocinic acid, benzoic acid is also used in reaction as end-capping reagent
To control molecular weight, and the glass transition temperature of polymer can be adjusted as needed.
The method that the present invention prepares hyperbranched polymeric monomer usually carries out condensation polymerization, solvent bag in the presence of a solvent
Include one or more of mixing of dimethylbenzene, toluene, ethylbenzene, butanone, cyclohexanone, butyl acetate, tetrahydrofuran, dioxanes etc.
Object.
Polymer provided by the invention containing dissaving structure is by above-mentioned hyperbranched polymeric monomer and vinyl monomer：Propylene
Esters of gallic acid monomer, styrene or maleic acid (ester) copolymerization obtain.The contents of ethylene of wherein hyperbranched polymeric monomer accounts for total list
The 0.1%~30% of the contents of ethylene (the amount ratio of substance) of body.
The preparation method of acrylate provided by the invention containing dissaving structure, comprises the following steps：
(1) according to the performance requirement to synthetic product, polyester-amides or polyester type hyperbranched polymeric monomer are selected as over-expense
Change the intermediate of acrylate polymer；
(2) according to the polyester-amides of selection or polyester type hyperbranched polymeric monomer, suitable solvent is selected；
(3) according to selected dicyandiamide solution, reaction temperature is determined；
(4) according to the performance requirement to synthetic product, appropriate acrylic acid (ester) class monomer is selected；
(5) according to the performance requirement to synthetic product, using the molecular weight of chain-transferring agent control product.
The present invention also provides the resin containing dissaving structure as solvent-borne type synthetic resin, in solvent-borne type or solvent-free painting
Purposes in material or adhesive.
The beneficial effects of the invention are as follows：Hyperbranched polymeric monomer provided by the invention, with conventional resins in identical solid content item
There are apparent low viscosity characteristics under part.The solid content of application product can be made to improve 10-30%.It is described depending on final purpose of usage
Hyperbranched polymeric monomer and other various additives such as dispersant, levelling agent, surface can be contained using its copolymer as key component
Tension regulator and filler etc..
The present invention is further carried out itself and acrylate monomer using first hyperbranched monomer of the synthesis with Copolymerization activity
Copolymerization introduces the method for hyperbranched monomer to reach in linear acrylate copolymer chain and changes molecular conformation, reduction viscosity, increasing
Add deliquescent purpose.In addition the function of further reactivity can be distributed in the molecular surface of the hyperbranched polymeric monomer
Group, the backbone that these functional groups are not curled are surrounded, and for the functional group of relatively traditional linear molecule, there is smaller position
Resistance, higher reactivity.Hyperbranched polymeric monomer is characterized by the methods of infrared, GPC, acid value and hydroxy value measuring, it is determined that
In the molecular structure of hyperbranched polymeric monomer there is the branched structure of three or three or more, and at least contain second on a branch
Alkenyl has multiple hydroxyls or carboxyl to be distributed along branch, and the hyperbranched polymeric monomer is applied to the synthesis of acrylate, prepares
Go out with superelevation degree of branching structure, the acrylate compared with low viscosity.
Description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the molecular structure of the polyester type hyperbranched polymeric monomer of an embodiment；
Fig. 2 is the molecular structure of the hyperbranched polymeric monomer of polyester-amides type of an embodiment；
Fig. 3 is the infrared spectrum of the polyester type hyperbranched polymeric monomer of an embodiment；
Fig. 4 is the infrared spectrum of the polyester-amides type branched macromonomers of an embodiment；
Fig. 5 is the viscosity comparison diagram of different acrylic resins.
Specific embodiment
Presently in connection with attached drawing, the present invention is described in detail.This figure is simplified schematic diagram, is only illustrated in a schematic way
The basic structure of the present invention, therefore it only shows composition related to the present invention.
Embodiment one:The synthesis of polyester type hyperbranched monomer
Embodiment one adds in flask using dimethylbenzene as solvent, by 92 grams of glycerine, and 296 are added portionwise when 100 DEG C small with 0.5
Gram phthalic anhydride makes its slow reaction, is gradually heating to 140 DEG C, and reflux keeps cooling down after ten minutes, and 100 DEG C add in 98 grams
Maleic anhydride is gradually heating to reflux state, is kept for 10 minutes.Cooling adds in 402 grams of trimethylolpropanes, is warming up to reflux
State keeps esterification to continue refuxing esterification to acid to 244 grams of benzoic acid of addition and 200 grams of lauric acid after below acid value 5mgKOH/g
Below value 5mgKOH/g.
Referring to Fig. 1, the molecular structure of the polyester type hyperbranched monomer for the present embodiment, is produced to intermediate during synthesis
The hydroxyl value of object and acid value analysis in table 1, referring to Fig. 3, the structural analysis infrared spectrum for product.
Further, the present embodiment synthesis hyper-branched polyester polymeric monomer using the glycerol molecule of trifunctional as core,
Synthesis experienced the half-esterification reaction of open loop of phthalic anhydride and glycerine, obtain product B-1；B-1 again with maleic anhydride into
Row open loop is half-esterification, obtains the branched shape molecule B-2 containing double bond and end carboxyl；B-2 reacts again with excessive trimethylolpropane,
The end carboxyl of branched shape molecule is made to change into the B-3 of terminal hydroxy group.Finally, with the unitary acid seal in a solvent with good solubility
Closing part divides terminal hydroxy group, obtains the polyester type hyperbranched molecule B-4 of terminal hydroxy group containing part and solubilizing group.
Since the substep synthesis of polyester type hyperbranched monomer is mainly esterification, and can be by system acid value and hydroxyl value
Detection characterize reaction step.From the analysis data of table 1, the hydroxyl value of product B-1 is 147.6, acid value 285.2, hydroxyl
Value is about the 1/2 of acid value, illustrates that the trihydroxylic alcohol in substance system has reacted about 2/3, this matches with the first step reaction of imagination.Production
The hydroxyl value of object B-2 is 4.7, and acid value more than 350 shows that hydroxyl fundamental reaction is complete, generates the change using carboxyl as major end group
Close object.The acid value of product B-3 is 3.9, and hydroxyl value is 410.7, illustrates that the end carboxyl of product B-2 is esterified completely substantially, is formed
Hydroxy-end capped product.Finally, it can be seen that the hydroxy radical content of B-4 has fallen to 134, and acid value is 4.7, is slightly had than B-3
It improves, shows the monocarboxylic acid sealing end that a part of hydroxyl of product is eventually adding.
The hydroxyl value of intermediate product is analyzed with acid value in 1. polyester type hyperbranched monomer building-up process of table
The polyester type hyperbranched polymeric monomer (B-4) of synthesis is characterized with infrared spectrum, sees Fig. 4.In 3515.1cm-1Place
It can be seen that hydroxyl characteristic peak, shows that product contains hydroxy functional group, in 1724.8cm-1It can see stronger ester carbonyl group at (wave number)
Resonance characteristics absorb, in 1268.5cm-1Place is observed that the C-O vibrations being connected on ester with carbonyl, and in 1070.4cm-1It can
To see the eigen vibration absworption peak of C-O in R-C-O, information above can relatively be accurately judged to containing esterification structure.In addition
It can be seen that 1646.9cm-1Locate unsaturation C=C vibrations and fingerprint region 978.4cm-1Trans double bond characteristic peak illustrates the compound
To contain trans double bond structure
The analysis and characterization of example two and embodiment three can be carried out in this way.
Embodiment two：The synthesis of polyester type hyperbranched monomer
Using dimethylbenzene as solvent, 92 grams of glycerine are added in into flasks, 292 are added portionwise when 100 DEG C small with 0.5 and restrains oneself two
Acid makes its slow reaction, is gradually heating to 140~240 DEG C and is back to acid value to reach specified value, cools down, 100 DEG C add in 98 grams it is suitable
Anhydride maleique is gradually heating to reflux state, is kept for 10 minutes.Cooling adds in 402 grams of trimethylolpropanes, is warming up to reflux
State keeps esterification to continue refuxing esterification to acid to 244 grams of benzoic acid of addition and 200 grams of lauric acid after below acid value 5mgKOH/g
Below value 5mgKOH/g.
Embodiment three：The synthesis of polyester type hyperbranched monomer
Using dimethylbenzene as solvent, 92 grams of glycerine are added in into flask, 296 grams of adjacent benzene two are added portionwise when 100 DEG C small with 0.5
Formic anhydride makes its slow reaction, and gradually 140 DEG C of reflux of heating keep cooling down after ten minutes, 100 DEG C of additions, 98 grams of maleic acids
Acid anhydride is gradually heating to reflux state, is kept for 10 minutes.Cooling adds in 402 grams of trimethylolpropanes, is warming up to reflux state, keeps ester
244 grams of benzoic acid and 284 grams of stearic acid are added in after changing to below acid value 5mgKOH/g, continue refuxing esterification to acid value 5mgKOH/g
Below.
Example IV：The synthesis of the hyperbranched monomer of poly- (ester-acid amide) type
Under nitrogen protection using N,N-dimethylformamide and a small amount of benzene as solvent, by 116 grams of maleic acids, 170 grams
Diethanol amine add in four-neck flask, cold oil bath in stir, slowly heat up after heat release is complete, 135 DEG C reflux 0.5 it is small when after
Start to survey acid value.Less than 100 DEG C are cooled to after acid value is down to 5mgKOH/g, 592 grams of phthalic anhydrides are added in, at 100 DEG C
Keep 0.5 it is small when, be warming up to 135 DEG C, when reflux 0.5 is small after start to survey acid value.Acid value cools down after dropping to below 264mgKOH/g
To less than 50 DEG C, add in 340 grams of diethanol amine, be to slowly warm up to 135 DEG C, when reflux 1 is small after start to survey acid value.Acid value is down to
Stop reaction after below 5mgKOH/g.
Its molecular structure such as Fig. 2, infrared spectrum are shown in Fig. 4.
Further, Fig. 2 is the design diagram of the hyperbranched polymeric monomer of poly- (ester-acid amide) type, and feature is to use more officials
Raw material can be rolled into a ball, with double bond containing dicarboxylic acids (maleic acid) for core, utilizes amido and carboxyl generation amide, anhydride group and hydroxyl
The reaction of base generation ester repeatedly successively extends molecule, forms dissaving structure, and carries multiple primary hydroxyls in molecular end.Over-expense
The synthesis for changing polyamide polymeric monomer experienced the dehydration amidation process of diethanol amine and maleic acid, with phthalic anhydride
Half-esterification process and amidation process with diethanol amine.Thus, the building-up process of hyperbranched poly (ester-acid amide) can
Replacing growth and decline and judge by ester during stepwise reaction and amide characteristic peak.
Fig. 4 is the infrared analysis collection of illustrative plates of hyperbranched poly (ester-acid amide) polymeric monomer of synthesis, 1629.6 from figure
cm- 1Place is it can be seen that the absworption peak of carbonyl, wave number 1629.6cm- 1Significantly lower than general ester carbonyl groupIn 1735cm- 1Characteristic absorption, this is related with the conjugation for the nitrogen-atoms that carbonyl is attached thereto.So can be with
It is judged as teritary amide baseAbsorption, it can thus be appreciated that generating expected amide product.From fingerprint region 960.4cm-1SeeCharacteristic absorption, it can be determined that be to have the structure of trans-2-butene, illustrate that maleic acid is sent out during amidated
The variation of cis-trans isomerism is given birth to.In 3359.4cm- 1Place has apparent O-H characteristic peaks to may determine that product contains hydroxyl.
1283.4cm-1、1260.3cm-1There are benzoic ether in many places such as CThe characteristic absorption peak of middle C-O-C.Therefore it can sentence
Fixed reaction is completed substantially according to design route, generates poly- (ester-acid amide) the type super branched molecule of hydroxyl.To embodiment five
Analysis can be carried out in this way with characterization.
Embodiment five：The synthesis of the hyperbranched monomer of poly- (ester-acid amide) type
Under nitrogen protection using N,N-dimethylformamide and a small amount of benzene as solvent, by 116 grams of maleic acids, 170 grams
Diethanol amine add in four-neck flask, cold oil bath in stir, slowly heat up after heat release is complete, 135 DEG C reflux 0.5 it is small when after
Start to survey acid value.Less than 100 DEG C are cooled to after acid value is down to 5mgKOH/g, 592 grams of phthalic anhydrides are added in, at 100 DEG C
Keep 0.5 it is small when, be warming up to 135 DEG C, when reflux 0.5 is small after start to survey acid value.Acid value cools down after dropping to below 264mgKOH/g
To less than 50 DEG C, add in 340 grams of diethanol amine, when 135 DEG C of reflux 0.5 are small after start to survey acid value.When acid value is down to
Be cooled to less than 100 DEG C after 5mgKOH/g, add in 196 grams of maleic anhydrides, be to slowly warm up to 135 DEG C, when reflux 1 is small after open
Begin to survey acid value.Acid value stops reaction after being down to below 5mgKOH/g.
Embodiment six：The synthesis of acrylic resin containing polyester type hyperbranched structure
A certain amount of dimethylbenzene is put into four-necked bottle and is warming up to reflux state, under nitrogen protection, dropwise addition prepares in proportion
Initiator (benzoyl peroxide or cumyl peroxide, dosage be amount of monomer 0.5%), acrylic acid, butyl acrylate,
Hydroxy-ethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, polyester type hyperbranched polymeric monomer are (by resin property requirement, often
The secondary hyperbranched polymeric monomer prepared with a kind of embodiment one to embodiment three, amount ratio be whole amount of monomer 20% or 30% or
40%), chain-transferring agent (lauryl mercaptan or beta -mercaptoethanol, dosage 1-2%), xylene solvent etc., delay when 3-5 is small
Slowly drip off, keep 0.5 it is small when after, add initiator and solvent, 1 is added dropwise when small.Vacuum removal after when keeping reaction 1 small again
Solvent.
Embodiment seven：The synthesis of acrylic resin containing poly- (ester-acid amide) type dissaving structure
A certain amount of dimethylbenzene is put into four-necked bottle, under nitrogen protection, is warming up to reflux state, dropwise addition prepares in proportion
Solvent and initiator, the hyperbranched polymeric monomer of poly- (ester-acid amide) type (point out example IV and embodiment five prepare it is hyperbranched
Polymeric monomer), butyl acrylate, hydroxypropyl acrylate, methyl methacrylate, styrene, the solution of the preparations such as chain-transferring agent, 3-
5 drip off when small, keep 0.5 it is small when after, with 1 it is small when drip second step initiator and solvent, then keep reaction 1 it is small when after vacuum
Remove solvent.Used initiator, chain-transferring agent and dosage are the same as embodiment six.
Embodiment eight：Application of the acrylic resin of dissaving structure in coating
Tested the hydroxy radical content of the acrylic resin containing polyester type hyperbranched structure that (measurement result is hydroxy radical content
2.8%) 3.5, then with part Amino resin or butylated amino resin are pressed:1-2.5:1 (solid masses ratio) mixture, is pressed
National standard making sheet film in design temperature with being toasted under the time (140 DEG C, 30mi n), and carries out its main performance
Detection.
After the hydroxy radical content of acrylic resin equally to containing poly- (ester-acid amide) type dissaving structure is tested, with
TDI-TMP addition products press 1:0.9~1.1 (- OH:- NCO) ratio mixture, it is main to its after dried coating film by national standard making sheet
Performance is detected.
It was found from testing result (see Fig. 5, table 2-3)：(1) viscosity of the acrylic resin with dissaving structure is less than and adopts
The conventional acrylic resin produced with conventional method；(2) by with dissaving structure acrylic resin prepare coating, with
The coating of (commercially available) preparation of conventional resins is compared, and on the premise of identical solid content, what viscosity was discharged when declining, using has
Solvent amount significantly declines, and can save organic solvent 40%；And drying temperature declines, drying time shortens；Hardness of film carries
It is high.All indexs are up to state standards requirement.
2. high solid car paint of table and the partial properties of traditional coating (finishing coat) compare
3. high solid car paint of table and the comparison of traditional coating (priming paint) partial properties
The present invention has been synthesized two kinds of inside using progressively development method and has been carried with double bond outside by new MOLECULE DESIGN
The hyperbranched polymeric monomer of hydroxyl, carboxyl isoreactivity functional group --- polyester-type and the hyperbranched polymeric monomer of polyester-amides type lead to
The methods of crossing infrared, GPC, acid value and hydroxy value measuring characterizes hyperbranched polymeric monomer and its building-up process.By two synthesized classes
Hyperbranched polymeric monomer is applied to the synthesis of acrylic resin, has prepared with superelevation degree of branching structure, the propylene compared with low viscosity
Acid ester resin.The organic solvent content of acrylate in the production and use process can be effectively reduced, is reduced to environment
Pollution.
Using above-mentioned desirable embodiment according to the invention as enlightenment, by above-mentioned description, relevant staff
Various changes and amendments can be carried out in without departing from the scope of the present invention completely.The technical scope of this invention is not
The content being confined on specification, it is necessary to which its technical scope is determined according to right.
Claims (9)
1. a kind of hyperbranched polymeric monomer, it is characterised in that：With the branched structure of three or three or more, and at least in a branch
Contain vinyl on chain, there is multiple hydroxyls or carboxyl to be distributed along branch.
2. hyperbranched polymeric monomer as described in claim 1, it is characterised in that：The hyperbranched polymeric monomer is polyester-type or polyamides
The hyperbranched polymeric monomer of amine type.
3. a kind of method for preparing hyperbranched polymeric monomer as claimed in claim 1 or 2, using the method for fed batch, through more
Step is obtained by the reaction, and comprises the following steps：
A, double bond, A monomer of functional group's number more than or equal to 2 and B monomer reaction of the functional group more than or equal to 2 will be contained, obtained
Molecular weight bigger and the C performed polymers containing double bond；
B, the C performed polymers further carry out polycondensation reaction with the B monomer, are increased the degree of branching of molecule, through excessive
One-step polycondensation finally obtains the hyperbranched polymeric monomer.
4. the method for hyperbranched polymeric monomer is prepared as claimed in claim 3, it is characterised in that：A monomers are described in a steps：Contain
There are double bond, maleic acid of functional group's number more than or equal to 2, maleic anhydride；The B monomer is：Functional group's number is big
In equal to 2 N,N-dimethylformamide, diethanol amine, maleic acid, glycerine, pentaerythrite, trimethylolpropane, neighbour
Phthalic acid, phthalic anhydride, maleic anhydride, trimellitic anhydride etc..
5. the method for hyperbranched polymeric monomer is prepared as claimed in claim 3, it is characterised in that：Condensation polymerization is described in b step
It is carried out in solvent xylene, toluene, ethylbenzene, butanone, cyclohexanone, butyl acetate, tetrahydrofuran Huo dioxanes.
6. a kind of acrylate containing dissaving structure, it is characterised in that：The acrylate tree containing dissaving structure
Fat is to be copolymerized to obtain with vinyl monomer by any one of the claim 1-5 hyperbranched polymeric monomers, the hyperbranched polymeric monomer
The mole of contained vinyl accounts for the 0.1%~30% of the vinyl mole of total monomer.
7. the acrylate containing dissaving structure as claimed in claim 6, it is characterised in that：The vinyl monomer is third
Olefin(e) acid esters monomer, styrene or maleic acid (ester).
8. a kind of preparation method of the acrylate containing dissaving structure as claimed in claim 6, comprises the following steps：
(1) according to the performance requirement to synthetic product, select polyester-amides or polyester type hyperbranched polymeric monomer as described containing super
The intermediate of the acrylate of branched structure；
(2) according to the polyester-amides of selection or polyester type hyperbranched polymeric monomer, suitable solvent is selected；
(3) according to selected dicyandiamide solution, reaction temperature is determined；
(4) according to the performance requirement to synthetic product, appropriate acrylic acid (ester) class monomer is selected；
(5) according to the performance requirement to synthetic product, using the molecular weight of chain-transferring agent control product.
9. the acrylate containing dissaving structure as claimed in claim 6, it is characterised in that：It is described to contain dissaving structure
Acrylate can be used for high solid self-drying paint, high solid baked paint, high solid two-component normal temperature cure
Coating and conduct adhesive use.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113430666A (en) * | 2021-06-29 | 2021-09-24 | 东华大学 | High-strength coarse denier polyvinyl alcohol fiber containing OH-HBP and preparation method thereof |
| CN113801306A (en) * | 2021-08-26 | 2021-12-17 | 江苏麒祥高新材料有限公司 | Polymaleic acid polyol ester and preparation method, loading method and application thereof |
| CN114276554A (en) * | 2021-12-22 | 2022-04-05 | 广东南海启明光大科技有限公司 | High-thixotropy and high-dispersion resin and silver paste, and preparation method and application thereof |
| CN115746319A (en) * | 2022-10-27 | 2023-03-07 | 优卡化学(上海)有限公司 | Hyperbranched acrylate polymer and preparation method and application thereof |
| CN116355231A (en) * | 2023-04-10 | 2023-06-30 | 四川双特科技有限公司 | Synthesis and preparation method of EB (electron beam) curing coating for metal coiled material |
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| CN1919893A (en) * | 2005-08-26 | 2007-02-28 | 中国科学院成都有机化学有限公司 | Hyperbranched great macromonomer, acrylate resin containing hyperbranched structure and preparation method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1919893A (en) * | 2005-08-26 | 2007-02-28 | 中国科学院成都有机化学有限公司 | Hyperbranched great macromonomer, acrylate resin containing hyperbranched structure and preparation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113430666A (en) * | 2021-06-29 | 2021-09-24 | 东华大学 | High-strength coarse denier polyvinyl alcohol fiber containing OH-HBP and preparation method thereof |
| CN113801306A (en) * | 2021-08-26 | 2021-12-17 | 江苏麒祥高新材料有限公司 | Polymaleic acid polyol ester and preparation method, loading method and application thereof |
| CN114276554A (en) * | 2021-12-22 | 2022-04-05 | 广东南海启明光大科技有限公司 | High-thixotropy and high-dispersion resin and silver paste, and preparation method and application thereof |
| CN115746319A (en) * | 2022-10-27 | 2023-03-07 | 优卡化学(上海)有限公司 | Hyperbranched acrylate polymer and preparation method and application thereof |
| CN115746319B (en) * | 2022-10-27 | 2023-08-25 | 优卡化学(上海)有限公司 | Hyperbranched acrylic ester polymer and preparation method and application thereof |
| CN116355231A (en) * | 2023-04-10 | 2023-06-30 | 四川双特科技有限公司 | Synthesis and preparation method of EB (electron beam) curing coating for metal coiled material |
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