CN108003337B - Hyperbranched star polymer of uV curable and its preparation method and application - Google Patents
Hyperbranched star polymer of uV curable and its preparation method and application Download PDFInfo
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- CN108003337B CN108003337B CN201711231344.3A CN201711231344A CN108003337B CN 108003337 B CN108003337 B CN 108003337B CN 201711231344 A CN201711231344 A CN 201711231344A CN 108003337 B CN108003337 B CN 108003337B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/78—Preparation processes
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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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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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
- C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
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Abstract
The present invention relates to technical field of coatings, provide a kind of hyperbranched star polymer and its preparation method and application of uV curable, the hyperbranched star polymer of the uV curable includes dissaving polymer kernel and linear polymer arm, and the dissaving polymer kernel and linear polymer arm pass through chemistry key connection；The terminal hydroxy group of the hyperbranched star polymer is modified to the group of carbon-carbon double bonds.Hyperbranched star polymer of the invention, with ability quick-setting under ultraviolet light, in the case where the linear polymeric arms degree of polymerization is suitable for, hyperbranched star polymer combines the advantages of dissaving polymer and linear polymer, improve levelability, solidification rate, hardness, adhesive force and the patience etc. of coating, in view of its good adhesive force and biological degradability, it is hopeful to be applied to the fields such as automobile and medical treatment.
Description
Technical field
The present invention relates to technical field of coatings, in particular to a kind of ultraviolet light solidifies the system of hyperbranched star polymer coating
Preparation Method, performance characterization and application prospect, the hyperbranched star polymer coating are hopeful to be applied to the neck such as automobile and medical treatment
Domain.
Background technique
Ultraviolet-curing paint is a kind of energy-saving and environment-friendly paint to grow up in nineteen sixties, since it is solid
Change that speed is fast, solvent content is few, low energy consumption and the advantages that having a wide range of application, to the research of ultraviolet-curing paint and answers in recent years
With increasing year by year.
Ultraviolet-curing paint is prepared usually using linear oligomer, is added into reactive diluent to reduce viscosity, and is lived
Property diluent increases the toxicity and pollution of coating.In recent years, dissaving polymer makes it due to its unique design feature
Study frontier (Prog.Org.Coat.2014,77,94 as photocureable coating；Prog.Org.Coat.2011,72,769；
Macromolecules.2011,44,878；Polym.Chem.2013,4,3105).The viscosity of dissaving polymer is significantly lower than
With the linear oligomer of molecular weight, the use of reactive diluent can be greatly reduced, volatile organic compounds is effectively reduced
(VOC) it discharges；Active end group is gathered in the spherical surface of dissaving polymer, substantially increases the solidification rate of coating；Over-expense
The branched structure of chemoattractant molecule can reduce cure shrinkage, improve adhesive force.However, the spherical structure of dissaving polymer is certain
Crosslinking steric hindrance is increased in degree, leads to unreacted functional group more than needed, and unreacted labile functional groups can reduce the steady of paint film
Qualitative and patience, therefore Hyperbranched Polymer has some limitations.
Summary of the invention
The present invention is in view of the shortcomings of the prior art, provide a kind of ultraviolet light solidification hyperbranched star polymer coating.The over-expense
Changing star polymer includes dissaving polymer kernel and linear polymer arm, can combine dissaving polymer and linear polymerization
The advantages of object.Dissaving polymer kernel can reduce system viscosity, provide functional group abundant and branched structure, linear polymerization
Object arm can reduce the crosslinking steric hindrance of system, improve the degree of cross linking of system, unreacted functional group be reduced, to improve the steady of paint film
Qualitative and patience.Therefore, in order to break through the limitation of linear polymer coating and Hyperbranched Polymer, the present invention is constructed
A kind of hyperbranched star polymer, using for ultraviolet-curing paint.
The present invention provides a kind of ultraviolet light solidification hyperbranched star polymer coating, to solve linear polymerization in the prior art
Object viscosity is big, dissaving polymer crosslinking steric hindrance is big and contains unreacted functional group, final to pollute environment or influence paint film property
Technical matters.
The present invention also provides the preparation methods of the hyperbranched star polymer of above-mentioned uV curable.
The present invention also provides above-mentioned ultraviolet light solidify the thermal stability of hyperbranched star polymer coating, hardness, adhesive force,
The performance characteristics such as patience and levelability.
The present invention also provides shadow of the degree of polymerization to paint film property that above-mentioned ultraviolet light solidifies hyperbranched star polymer coating
It rings.
The purpose of the present invention is what is be achieved through the following technical solutions:
In a first aspect, the present invention provides a kind of hyperbranched star polymer of uV curable, including hyperbranched poly
Object kernel and linear polymer arm are closed, the dissaving polymer kernel and linear polymer arm pass through chemistry key connection；It is described
The terminal hydroxy group of hyperbranched star polymer is modified to the group of carbon-carbon double bonds.
Preferably, the dissaving polymer kernel is hyper-branched polyester kernel.
It is highly preferred that it is four generation hyper-branched polyester kernels, per molecule on average that the dissaving polymer kernel, which is core,
Containing 64 hydroxyls, theoretical molecular weight 7214g/mol.
Preferably, the linear polymer arm is biodegradable polycaprolactone arm, and the degree of polymerization is 15~25.It is described
The degree of polymerization regulated and controled according to coating practical application request.
It is highly preferred that the degree of polymerization is 20, comprehensive performance is optimal.
Preferably, the method that the terminal hydroxy group of the hyperbranched star polymer is modified to the group of carbon-carbon double bonds are as follows: will
Hyperbranched star polymer and excessive blocking agent reaction, are blocked with methacrylic acid group；The end-capping reagent is methyl-prop
Olefin(e) acid acid anhydride.
Second aspect, the present invention provides a kind of preparation method of the hyperbranched star polymer of uV curable, packets
Include following steps:
(1) hyper-branched polyester and 6-caprolactone are subjected to ring-opening polymerization under catalyst a effect, obtain hyperbranched star
Shape polymer one；
(2) hyperbranched star polymer one and end-capping reagent carry out ester exchange reaction, dead-end polymerization under the action of catalyst b
Object obtains the hyperbranched star polymer two that end group is carbon-carbon double bonds group, the i.e. cured hyperbranched star of ultraviolet light
Shape polymer.
Preferably, the molar feed ratio of amount of hydroxyl groups and 6-caprolactone contained by hyper-branched polyester described in step (1) is 1:15
~1:25；In step (2), the molar feed ratio of hyper-branched polyester institute hydroxyl described in the end-capping reagent and step (1) is 2:
1。
Preferably, catalyst a described in step (1) is Sn (Oct)2, catalyst a rubs with hyper-branched polyester institute's hydroxyl
Your feed ratio is 1:20；Catalyst b described in step (2) be triethylamine and 4-dimethylaminopyridine, the triethylamine and over-expense
The molar feed ratio for changing polyester institute hydroxyl is 3:1, mole of the 4-dimethylaminopyridine and hyper-branched polyester institute hydroxyl
Feed ratio is 1:2.5.
Preferably, ring-opening polymerisation described in step (1) is bulk polymerization, ester exchange reaction institute described in step (2)
It is methylene chloride with solvent.
Preferably, ring-opening polymerization temperature described in step (1) is 130 DEG C, and the reaction time is 5 hours；In step (2)
The ester exchange reaction is to react under ice bath, and the reaction time is 5 hours.
Preferably, in step (1), vacuumized before the reaction, and react under nitrogen protection, it is ensured that anhydrous and oxygen-free it is anti-
Answer environment；The 6-caprolactone uses after vacuum distillation purification.
Preferably, the reaction products therefrom cold methanol through step (1): ether=1:1 mixed organic solvents into
Row precipitating, filters later, and 35 DEG C of drying obtain hyperbranched star polymer one；
The reaction products therefrom through step (1) is precipitated with cold methanol, is filtered later, and 35 DEG C of drying obtain hyperbranched star
Shape polymer two.
The third aspect, the present invention provides a kind of hyperbranched star polymer of uV curable in preparation UV light
Change the application in coating.It is hopeful to be applied to vapour with preferable levelability, solidification rate, hardness, adhesive force and patience etc.
The fields such as vehicle and medical treatment.
Fourth aspect, the present invention provides a kind of preparation method of ultraviolet-curing paint, including using it is above-mentioned can be purple
The hyperbranched star polymer of outer photocuring mixed with photoinitiator to get.
In the ultraviolet-curing paint, the concentration of hyperbranched star polymer is 1.0~8.0mmol/L or hyperbranched
The mass percentage of star polymer is 10~80%.
Preferably, the photoinitiator is 2- hydroxy-2-methyl propiophenone, and dosage is 3% mass fraction.
Ultraviolet-curing paint above-mentioned is coated, crosslinking curing is carried out under ultraviolet lighting, obtains photo-curing paint
Film.The ultraviolet lighting time is 5 minutes；The power of ultraviolet light illuminator is 300W；Ultraviolet lighting wavelength is 365nm.
Hyperbranched star polymer of the present invention, can rapid curing under ultraviolet light, polymerize in linear polymeric arms
In the case that degree is suitable for, the advantages of hyperbranched star polymer combines dissaving polymer and linear polymer, the stream of coating
Levelling, solidification rate, hardness, adhesive force and patience etc. are improved.
The dissaving polymer is intermolecular almost without chain entanglement due to its unique three-dimensional spherical structure, so that over-expense
The viscosity of fluidized polymer is significantly lower than the linear oligomer with molecular weight；And the global molecular surface of dissaving polymer is with rich
Rich functional group, therefore, the ultraviolet light solidify hyperbranched star polymer coating, and hyper-branched polyester kernel significantly reduces
The viscosity of coating, improves the levelability and solidification rate of coating.Linear polymer arm can reduce the crosslinking steric hindrance of system,
The degree of cross linking of raising system reduces unreacted functional group, and therefore, the ultraviolet light solidifies hyperbranched star polymer coating,
Its polycaprolactone arm improves the stability and patience of paint film.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, hyperbranched star polymer of the invention, due to being twined between the hyper-branched polyester inner core molecule that uses almost without chain
Knot, viscosity is significantly lower than the linear oligomer with molecular weight, can effectively reduce the dosage of reactive diluent and solvent, thus has
Effect reduces the discharge of VOC；
2, hyperbranched star polymer of the invention, as a kind of ultraviolet-curing paint, curing rate is fast, energy consumption
Considerably less than heat drying can be used for the coating of various thermo-sensitive materials；
3, ultraviolet light of the invention solidifies hyperbranched star polymer coating, including dissaving polymer kernel with can biology
The linear polymer arm of degradation, between the two by chemistry key connection, with methacrylate to hyperbranched star polymer
Terminal hydroxy group modified, can be in conjunction with dissaving polymer and linear polymer the advantages of.Dissaving polymer kernel can
Reducing system viscosity, offer functional group abundant and branched structure, linear polymer arm can reduce the crosslinking steric hindrance of system, mentions
The degree of cross linking of high system reduces unreacted functional group, to improve the stability and patience of paint film.Therefore, over-expense of the invention
Change star polymer and breach the limitation of linear polymer coating and Hyperbranched Polymer, have preferable levelability,
Solidification rate, hardness, adhesive force and patience etc., and there is certain biological degradability, it is hopeful to be applied to automobile and medical treatment etc.
Field；
4, ultraviolet light of the invention solidifies hyperbranched star polymer coating, probed into its comprehensive performance it is optimal when polymerization
Degree compares by hot property and paint film property experiment, when the degree of polymerization of polycaprolactone is 20, has both improved the levelability of coating
And curing rate, in turn ensure hardness, adhesive force and the patience of coating；
5, the hyper-branched polyester used in the present invention is a kind of comparative maturity and commercialized dissaving polymer,
With preferable cost performance；G-polycaprolactone has been greatly reduced the cost of coating while improving paint film property；Cause
And ultraviolet light of the invention solidifies hyperbranched star polymer coating cost performance with higher, is hopeful to be applied to actual
In industrial production.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the schematic diagram of the synthesis grafting dissaving polymer of embodiment 1；
Fig. 2 is the grafting dissaving polymer H that embodiment 1 synthesizes40-star-PCL20's1H NMR spectra；
Fig. 3 is the grafting dissaving polymer H that embodiment 1 synthesizes40-star-PCL20's13C NMR spectra；
Fig. 4 is the methacrylate sealing end grafting dissaving polymer H that embodiment 1 synthesizes40-star-PCL20- MAC's1H NMR spectra；
Fig. 5 is the methacrylate sealing end grafting dissaving polymer H that embodiment 1 synthesizes40-star-PCL20-MAC
's13C NMR spectra；
Fig. 6 is the grafting dissaving polymer H that embodiment 1 synthesizes40-star-PCL20DSC data figure；
Fig. 7 is the H that embodiment 1 synthesizes40、H40-star-PCL20、H40- MAC and H40-star-PCL20The thermal weight loss of-MAC
Curve.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Hyperbranched star polymer in the present invention, including dissaving polymer kernel and biodegradable linear polymerization
Object arm is modified with terminal hydroxy group of the methacrylic anhydride to hyperbranched star polymer.Hyperbranched star polymerization of the invention
Object has quick-setting ability under ultraviolet light, in the case where the linear polymeric arms degree of polymerization is suitable for, hyperbranched star polymerization
Object combines the advantages of dissaving polymer and linear polymer, improves the levelability, solidification rate, hardness, attachment of coating
Power and patience etc..
And the dissaving polymer, due to its unique three-dimensional spherical structure, intermolecular almost without chain entanglement, viscosity is bright
The aobvious linear oligomer lower than with molecular weight；And global molecular surface has functional group abundant, therefore, the UV light
Change hyperbranched star polymer coating, hyper-branched polyester kernel significantly reduces the viscosity of coating, improves the levelling of coating
Property and solidification rate.Linear polymer arm can reduce the crosslinking steric hindrance of system, improve the degree of cross linking of system, reduce unreacted official
It can roll into a ball, therefore, the ultraviolet light solidifies hyperbranched star polymer coating, and polycaprolactone arm improves the stability of paint film
And patience.Compare by hot property and paint film property experiment, when the degree of polymerization of polycaprolactone is 20, comprehensive performance is optimal.
Compared with prior art, ultraviolet light of the present invention solidifies hyperbranched star polymer coating, breaches linear
It is big, hyperbranched to solve linear polymer viscosity in the prior art for the limitation of polymer coating and Hyperbranched Polymer
Crosslinked polymer steric hindrance is big and contains unreacted functional group, the final technical matters for polluting environment or influencing paint film property, and
With preferable levelability, solidification rate, hardness, adhesive force and patience etc..
Embodiment 1
The preparation method that the ultraviolet light of the present embodiment solidifies hyperbranched star polymer coating includes the following steps:
(1) it is grafted the preparation of dissaving polymer:
By taking the preparation method when degree of polymerization of polycaprolactone is 20 as an example.As shown in Figure 1, by four generation hyper-branched polyester H40
The purified 6-caprolactone (16.0g, 142mmol) of (0.800g, hydroxyl containing 7.10mmol) and vacuum distillation is added in reaction flask,
Under nitrogen atmosphere, make H40It is dissolved completely in 6-caprolactone, is warming up to 130 DEG C, be added catalyst Sn (Oct)2, catalyst with
The molar feed ratio of hyper-branched polyester institute hydroxyl is 1:20, causes ring-opening polymerization, and stirring is reacted 5 hours, obtained sticky
Liquid.After being cooled to room temperature, into reaction flask plus tetrahydrofuran dissolution, the precipitating in 400mL cold methanol/ether (1:1) are filtered
After obtain white solid particle, dry 24 hours at 35 DEG C, obtain hyperbranched star polymer one, be labeled as H40-star-
PCL20(83.2%yield).
As shown in Fig. 2, the hydrogen spectrum nuclear-magnetism structure confirmation data of the polymer is as follows:1H NMR(CDCl3,ppm):7.29,
4.10-4.07,3.69-3.66,2.35-2.31,1.68-1.65,1.44-1.40,1.27。
As shown in figure 3, the carbon spectrum nuclear-magnetism structure confirmation data of the polymer is as follows:13C NMR(CDCl3,ppm):
173.59,77.03,63.91,34.04,28.45,25.34,24.44。
In kind preparing the degree of polymerization is 15 (using four generation hyper-branched polyester H40(0.800g, hydroxyl containing 7.10mmol)
Reacted with purified 6-caprolactone (12.0g, 106.5mmol) is evaporated under reduced pressure) and 25 (use four generation hyper-branched polyester H40
(0.800g, hydroxyl containing 7.10mmol) and the purified 6-caprolactone (20g, 177.5mmol) of vacuum distillation are reacted) connect
Branch dissaving polymer, is labeled as H40-star-PCL15And H40-star-PCL25。
(2) methacrylate sealing end grafting dissaving polymer:
By taking the preparation method when degree of polymerization of polycaprolactone is 20 as an example.The H that will be prepared40-star-PCL20
(5.00g, hydroxyl containing 7.10mmol) is dissolved in 15mL methylene chloride, under nitrogen atmosphere, catalyst of triethylamine is added
(0.607g, 6.00mmol) and 4-dimethylaminopyridine (0.100g, 0.82mmol), triethylamine and hyper-branched polyester institute hydroxyl
Molar feed ratio be 3:1, the molar feed ratio of 4-dimethylaminopyridine and hyper-branched polyester institute hydroxyl is 1:2.5.Reaction
Access is equipped with the dry ball of anhydrous calcium chloride on bottle, and reaction carries out under ice bath.The methyl-prop in 3mL methylene chloride will be diluted in
Olefin(e) acid acid anhydride (0.617g, 4.00mmol) is added dropwise in reaction flask, and stirring reacts 3 hours, obtains light yellow viscous liquid.To
Methylene chloride cut back is added in reaction flask, is precipitated in 400mL cold methanol, filters, is obtained with after cold milli-Q water 3 times
White solid particle, it is 24 hours dry at 35 DEG C, hyperbranched star polymer two is obtained, H is labeled as40-star-PCL20-
MAC (87.6%yield).
As shown in figure 4, the hydrogen spectrum nuclear-magnetism structure confirmation data of the polymer is as follows:1H NMR(CDCl3,ppm):7.29,
6.09,5.55,4.08-4.04,2.32-2.29,1.67-1.63,1.40-1.38,1.25。
As shown in figure 5, the carbon spectrum nuclear-magnetism structure confirmation data of the polymer is as follows:13C NMR(CDCl3,ppm):
173.81,125.53,77.59,77.27,64.38,34.33,28.55,25.73,24.78。
In kind prepare the grafting dissaving polymer that the methacrylate that the degree of polymerization is 15 and 25 blocks, label
For H40-star-PCL15- MAC and H40-star-PCL25-MAC。
In addition, in order to the characteristics of embodying g-polycaprolactone arm and compare, equally synthesis H40- MAC directly uses first
Base acrylic anhydride modifies four generation hyper-branched polyester H40Terminal hydroxy group.
(3) the hyperbranched star polymeric U photo-curing paint film preparation of mass fractions (for 10%) such as:
Take H40-star-PCLn(0.5g) is dissolved in 3mL methylene chloride, and the photoinitiator 2- hydroxyl-of 3% mass fraction is added
Solution is applied to the tinplate sheet by cleaning treatment with the spreading rod of 30 μ m-thicks by 2- methyl phenyl ketone, be placed on power 300W,
It is irradiated 5 minutes under the ultraviolet lamp of wavelength 365nm.4 kinds of paint films, i.e. H are prepared altogether40-MAC、H40-star-PCL15-MAC、H40-
star-PCL20- MAC and H40-star-PCL25-MAC。
In the case where equal mass fractions, the degree of polymerization of polycaprolactone arm is smaller, and the content of hyper-branched polyester is got in system
Height, the characteristics of hyper-branched polyester kernel can be highlighted.
(4) the hyperbranched star polymeric U photo-curing paint film preparation of equimolar concentration (by taking 1.0mmol/L as an example):
Take H40-star-PCLn(3 μm of ol) is dissolved in 3mL methylene chloride, and the photoinitiator 2- hydroxyl-of 3% mass fraction is added
Solution is applied to the tinplate sheet by cleaning treatment with the spreading rod of 30 μ m-thicks by 2- methyl phenyl ketone, be placed on power 300W,
It is irradiated 5 minutes under the ultraviolet lamp of wavelength 365nm.4 kinds of paint films, i.e. H are prepared altogether40-MAC、H40-star-PCL15-MAC、H40-
star-PCL20- MAC and H40-star-PCL25-MAC。
In the case where equimolar concentration, the content of hyper-branched polyester is identical in system, and difference is only that polycaprolactone arm
Length, it is thus possible to the characteristics of embodying g-polycaprolactone arm.
Performance evaluation and compliance test result:
1) nuclear-magnetism, GPC, DSC and TGA test are carried out to hyperbranched star polymer prepared by embodiment 1, as a result as follows:
H is calculated by hydrogen spectrum nuclear-magnetism40-star-PCL15、H40-star-PCL20And H40-star-PCL25In average each H40Institute
The number of the arm containing polycaprolactone and the degree of polymerization, the molecular weight of polycaprolactone arm, specific data are listed in table 1.H40-star-PCLn
Nuclear magnetic spectrogram in, as shown in Fig. 2, signal peak at 1.27ppm is the methyl proton peak in hyper-branched polyester, at 3.67ppm
Signal peak be the methylene adjacent with terminal hydroxy group proton peak, 2.34ppm place signal peak for polycaprolactone arm repetition list
The proton peak of the methylene adjacent with ester group in member can be obtained averagely every by comparing the integral area of the above two signal peaks
A H40The number of contained polycaprolactone arm, then the ratio of the two signal peak integral area is H40-star-PCLnThe degree of polymerization,
The degree of polymerization is calculated as the result is shown and the theoretical degree of polymerization is close.
Table 1
To H40、H40-star-PCL15、H40-star-PCL20、H40-star-PCL25、H40-MAC、H40-star-PCL15-
MAC、H40-star-PCL20- MAC and H40-star-PCL25- MAC carries out DSC test.About 7mg sample is weighed, is cooled to -50 DEG C,
150 DEG C are warming up to, stablizes 1 minute, to eliminate thermal history, is cooled to -50 DEG C, is stablized 1 minute, then be warming up to 150 DEG C, heating speed
Rate and rate of temperature fall are 10 DEG C/min.H40-star-PCL20DSC test curve as shown in fig. 6, all samples crystallization
Degree, melting origin temp, fusing point, glass transition temperature TgIt is listed in table 2.Since polycaprolactone is a kind of hemicrystalline polymerization
Object, therefore with the increase of the polycaprolactone degree of polymerization, the crystallinity of hyperbranched star polymer increases, with 166.5J/g when calculating
Melting heat as 100% crystallinity；The fusing point of polycaprolactone is 60~63 DEG C, TgIt is -60 DEG C, with the increasing of polycaprolactone arm
Long, the molecular weight of hyperbranched star polymer increases, flexibility improves, therefore fusing point increases, TgIt reduces；Methacrylic acid anhydride modification
Hyperbranched star polymer, branch terminals introduce ester group, the decline of end group polarity, and the soft segment in molecule increases, thus Tg
Decline.
Table 2
| Sample | Crystallinity (%) | It melts origin temp (DEG C) | Fusing point (DEG C) | Tg(℃) |
| H40 | 19 | 35.2 | 40.3 | -6.40 |
| H40-star-PCL15 | 44 | 45.4 | 51.3 | -8.55 |
| H40-star-PCL20 | 46 | 49.6 | 53.5 | -8.84 |
| H40-star-PCL25 | 47 | 50.9 | 55.6 | -10.2 |
| H40-MAC | 15 | 28.1 | 35.6 | -8.42 |
| H40-star-PCL15-MAC | 28 | 46.8 | 51.2 | -8.93 |
| H40-star-PCL20-MAC | 31 | 50.1 | 55.5 | -9.08 |
| H40-star-PCL25-MAC | 33 | 50.6 | 56.0 | -10.5 |
To H40、H40-star-PCL15、H40-star-PCL20、H40-star-PCL25、H40-MAC、H40-star-PCL15-
MAC、H40-star-PCL20- MAC and H40-star-PCL25- MAC carries out TGA test.Sample quality about 5mg, in nitrogen atmosphere
Under, 600 DEG C are heated to from 50 DEG C with the rate of 20 DEG C/min, measures the thermal stability of sample.H40、H40-star-PCL20、H40-
MAC and H40-star-PCL20The thermogravimetric curve of-MAC is as shown in fig. 7, the thermal weight loss 10%, 50% and 90% of all samples
Temperature is listed in table 3, it is known that all samples have preferable thermal stability.G-polycaprolactone arm, hyperbranched star polymer
Heat decomposition curve shows as two sections, i.e. polycaprolactone and two sections of hyper-branched polyester, the successful grafting of side illustration polycaprolactone arm；
With methacrylic anhydride to hyperbranched star polymer end hydroxyl modification after, thermal decomposition temperature has obvious raising, be because
The methacrylate of modified end group has the function of crosslinking, crosslinks in thermal histories, and global molecular will be easier to decompose
Ester bond package in the molecule, therefore, thermal stability improve.
Table 3
| Sample | T10%/℃ | T50%/℃ | T90%/℃ |
| H40 | 293 | 325 | 353 |
| H40-star-PCL15 | 280 | 341 | 383 |
| H40-star-PCL20 | 274 | 338 | 410 |
| H40-star-PCL25 | 289 | 335 | 402 |
| H40-MAC | 342 | 382 | 396 |
| H40-star-PCL15-MAC | 349 | 387 | 405 |
| H40-star-PCL20-MAC | 363 | 408 | 429 |
| H40-star-PCL25-MAC | 358 | 399 | 423 |
2) the hyperbranched star polymer prepared to embodiment 1 is coated, ultraviolet light solidifies, and carries out performance to paint film
Test, as a result as follows:
The H of the mass fractions such as preparation40-MAC、H40-star-PCL15-MAC、H40-star-PCL20- MAC and H40-star-
PCL25Four kinds of paint films of-MAC.In the case where equal mass fractions, the degree of polymerization of polycaprolactone arm is smaller, hyper-branched polyester in system
Content it is higher, the characteristics of hyper-branched polyester kernel can be highlighted.It is coated with the spreading rod of 30 μ m-thicks, the film thickness of preparation
It is 30 μm.The characteristics of due to dissaving polymer low viscosity, coating of the invention does not add any reactive diluent.To four
Kind hyperbranched star polymer paint film carries out hardness, adhesive force, acid resistance, alkali resistance, levelability and the test of curing time point
Analysis, test result are listed in table 4.Determination of Hardness method refers to GB/T6739-2006, and adhesive force measuring method refers to GB/T 1720-
79, resistance to acid and alkali measuring method refers to GB/T 1763-79.As can be seen that polycaprolactone arm is shorter, the hardness of paint film, attachment
Power, levelability and solidification rate performance are better, this is because polycaprolactone arm is shorter in the case where equal mass fractions, over-expense
The relative amount for changing polyester is higher, and the viscosity of system is lower, and the functional group content in system is higher, has the methyl of crosslinking function
Acrylate end groups are more, thus crosslink density is bigger, and the C=C double bond of hyper-branched polyester is mainly distributed on global molecular
Surface, when carrying out ultraviolet light solidification, dissaving structure is conducive to the progress of cross-linking reaction, so that solidification rate improves, and holds
Fine and close cross-linked network is easily formed, so hardness of paint film, adhesive force, levelability and solidification speed more than dissaving structure content
Rate performance is more preferable.But simultaneously as can be seen that polycaprolactone arm is shorter, the acid resistance and alkali resistance of paint film are poorer, this is because containing
There is the dissaving structure of too high amount, possess functional group more than needed, and the crosslinking steric hindrance between global molecular is greater than between linear molecule
Crosslinking steric hindrance, cause to reduce the acid resistance and alkali resistance of paint film containing unreacted C=C double bond more than needed in paint film.This reality
It applies the advantages of the paint film property test experiments of example have fully demonstrated dissaving structure and disadvantage.
Table 4
" levelability, acid resistance, alkali resistance " is best with 10 in table 4, and the smaller expression performance of numerical value is poorer.
Prepare the H of equimolar concentration40-MAC、H40-star-PCL15-MAC、H40-star-PCL20- MAC and H40-star-
PCL25Four kinds of paint films of-MAC.In the case where equimolar concentration, the content of hyper-branched polyester is identical in system, and difference is only that poly-
The length of caprolactone arm, it is thus possible to the characteristics of embodying g-polycaprolactone arm.It is coated with the spreading rod of 30 μ m-thicks, due to matter
It is different to measure score, film thickness is all different, and polycaprolactone arm is longer, and mass fraction is bigger, and film thickness is bigger.Due to over-expense
The characteristics of fluidized polymer low viscosity, coating of the invention do not add any reactive diluent.Four kinds of hyperbranched stars are polymerize
Object paint film equally carries out hardness, adhesive force, acid resistance, alkali resistance, levelability and the test analysis of curing time, test result column
In table 5.As can be seen that the degree of polymerization of polycaprolactone arm is bigger, hardness, adhesive force, acid resistance, alkali resistance and the solidification speed of paint film
It is better to spend performance, this is because the hyperbranched poly ester content in system is identical, thus functional group in the case where equimolar concentration
Content is identical, and with the growth of polycaprolactone arm, the mass fraction of system increases, and solvent content is reduced, while soft segment increases
Add, greatly reduce crosslinking steric hindrance, when carrying out ultraviolet light solidification, polycaprolactone arm improves the degree of cross linking of reaction, improves
The density of cross-linked network structure effectively reduces unreacted C=C double bond more than needed in system, so the paint of polycaprolactone brachium
Film hardness, adhesive force, acid resistance, alkali resistance and curing rate performance are more preferable.But simultaneously as can be seen that the polymerization of polycaprolactone arm
Degree is bigger, and the levelability of paint film is poorer, this is because the degree of polymerization is bigger, linear molecule proportion is bigger, and molecular weight is bigger, body
The viscosity of system is bigger, thus g-polycaprolactone arm causes the levelability of paint film to be lost.The paint film property of the present embodiment is surveyed
The advantages of examination experiment has fully demonstrated polycaprolactone arm and disadvantage.
Table 5
" levelability, acid resistance, alkali resistance " is best with 10 in table 5, and the smaller expression performance of numerical value is poorer.
It is in table 5 the results show that three kinds of hyperbranched star polymer coatings and H produced by the present invention40It compares, it is hardness, attached
Put forth effort, resistance to acid and alkali has promotion.Illustrate to be prepared into after hub-and-spoke configuration, main advantage is that crosslinking when reducing solidification
Steric hindrance improves cross-linking reaction degree, reduces extra functional group, to improve performance.
H is shown in table 440Performance it is more excellent, be due to hyperbranched poly in the case where equal mass fractions, in four groups of samples
Ester content difference is excessive, and variable is not unique, therefore the characteristics of major embodiment hyper-branched polyester, is difficult the characteristics of embodying PCL arm.
Therefore, in table 5, we control H in sample40Content it is identical, the characteristics of to embody PCL arm.
Four kinds of paint films in the present embodiment are each advantageous, are hopeful to be applied in different fields.For comprehensive comparison, when
When the degree of polymerization of polycaprolactone is 20, H40-star-PCL20- MAC made paint film has optimal comprehensive performance.
Hyper-branched polyester H used in the present invention40It is a kind of comparative maturity and commercialized dissaving polymer,
With preferable cost performance；G-polycaprolactone has been greatly reduced the cost of coating while improving paint film property；This hair
Bright hyperbranched star polymer coating effectively reduces the dosage of reactive diluent and solvent, can be effectively reduced the discharge of VOC；
Thus, ultraviolet light of the invention solidifies hyperbranched star polymer coating cost performance with higher, is hopeful to be applied to reality
Industrial production in.
Offer one kind ultraviolet light that the present invention innovates solidifies hyperbranched star polymer coating, dissaving polymer kernel with
Linear polymer arm is modified by chemistry key connection with terminal hydroxy group of the methacrylic anhydride to hyperbranched star polymer,
Assign its ultraviolet light solidification function.The characteristics of present invention combination dissaving polymer and linear polymer coating, utilization is hyperbranched
The advantage of polymer low viscosity, the abundant and spherical branched structure of functional group, and utilize the flexible height of linear polymer and crosslinking steric hindrance
Small advantage, be prepared for can rapid curing under ultraviolet light, and there is preferable levelability, hardness, solidification rate, adhesive force, resistance to
The performances hyperbranched star polymer coatings such as acid and alkali resistance, and the degree of polymerization of linear polymer has been probed into coating property
It influences.Based on its good adhesive force and biological degradability and higher cost performance, it is hopeful to be applied to automobile and medical treatment etc.
Field.
Under the teaching of the present invention and the above embodiments, those skilled in the art are easy to it is envisioned that cited by the present invention
Or each raw material enumerated or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention and each original
The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (8)
1. a kind of hyperbranched star polymer of uV curable, which is characterized in that including dissaving polymer kernel and line
Property polymeric arms, the dissaving polymer kernel and linear polymer arm pass through chemistry key connection；The hyperbranched star is poly-
The terminal hydroxy group for closing object is modified to the group of carbon-carbon double bonds；
The linear polymer arm is biodegradable polycaprolactone arm, and the degree of polymerization is 15~25；
The dissaving polymer kernel is hyper-branched polyester kernel.
2. the hyperbranched star polymer of uV curable as described in claim 1, which is characterized in that the hyperbranched star
The method that the terminal hydroxy group of shape polymer is modified to the group of carbon-carbon double bonds are as follows: by hyperbranched star polymer and excessive sealing end
Agent reaction；The end-capping reagent is methacrylic anhydride.
3. a kind of preparation side of such as hyperbranched star polymer of uV curable of any of claims 1-2
Method, which comprises the following steps:
(1) hyper-branched polyester and 6-caprolactone are subjected to ring-opening polymerization under catalyst a effect, it is poly- obtains hyperbranched star
Close object one；
(2) hyperbranched star polymer one and end-capping reagent carry out ester exchange reaction under the action of catalyst b, terminated polymer,
Obtain the hyperbranched star polymer two that end group is carbon-carbon double bonds group, the i.e. hyperbranched star of the uV curable
Polymer.
4. the preparation method of the hyperbranched star polymer of uV curable as claimed in claim 3, which is characterized in that step
Suddenly the molar feed ratio of amount of hydroxyl groups and 6-caprolactone contained by hyper-branched polyester described in (1) is 1:15~1:25；In step (2),
The molar feed ratio of hyper-branched polyester institute hydroxyl described in the end-capping reagent and step (1) is 2:1.
5. the preparation method of the hyperbranched star polymer of uV curable as claimed in claim 3, which is characterized in that step
Suddenly catalyst a described in (1) is Sn (Oct)2, the molar feed ratio of catalyst a and hyper-branched polyester institute hydroxyl is 1:20；Step
Suddenly catalyst b described in (2) is triethylamine and 4-dimethylaminopyridine, and the triethylamine rubs with hyper-branched polyester institute's hydroxyl
Your feed ratio is 3:1, and the molar feed ratio of the 4-dimethylaminopyridine and hyper-branched polyester institute hydroxyl is 1:2.5；
Ring-opening polymerisation described in step (1) is bulk polymerization, and ester exchange reaction solvent for use described in step (2) is dichloro
Methane.
6. the preparation method of the hyperbranched star polymer of uV curable as claimed in claim 3, which is characterized in that step
Suddenly ring-opening polymerization temperature described in (1) is 130 DEG C, and the reaction time is 5 hours；Ester exchange reaction described in step (2) is
It is reacted under ice bath, the reaction time is 5 hours.
7. a kind of hyperbranched star polymer of uV curable as described in claim 1 is preparing ultraviolet-curing paint
In application.
8. a kind of preparation method of ultraviolet-curing paint, which is characterized in that including described in any item using claim 1-3
The hyperbranched star polymer of uV curable mixed with photoinitiator to get；
In the ultraviolet-curing paint, the concentration of hyperbranched star polymer is 1.0~8.0mmol/L or hyperbranched star
The mass percentage of polymer is 10~80%.
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