CN108003337A - 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
- Publication number
- CN108003337A CN108003337A CN201711231344.3A CN201711231344A CN108003337A CN 108003337 A CN108003337 A CN 108003337A CN 201711231344 A CN201711231344 A CN 201711231344A CN 108003337 A CN108003337 A CN 108003337A
- Authority
- CN
- China
- Prior art keywords
- polymer
- hyperbranched
- hyperbranched star
- star polymer
- curable
- 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
Classifications
-
- 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
-
- 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
- C08G63/02—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
-
- 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
- C08G63/78—Preparation processes
-
- 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
- C08G63/78—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
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to technical field of coatings, provide hyperbranched star polymer of a kind of uV curable and its preparation method and application, the hyperbranched star polymer of the uV curable includes dissaving polymer kernel and linear polymer arm, and the dissaving polymer kernel passes through chemical key connection with linear polymer arm；The terminal hydroxy group of the hyperbranched star polymer is modified to the group of carbon-carbon double bonds.The hyperbranched star polymer of the present invention, with quick-setting ability under ultraviolet light, in the case where the linear polymeric arms degree of polymerization is suitable, hyperbranched star polymer combines the advantages of dissaving polymer and linear polymer, improve levelability, solidification rate, hardness, adhesive force and patience of coating etc., in view of its good adhesive force and biological degradability, are 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, more particularly to a kind of ultraviolet light cures 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 technology
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, energy consumption is low and the advantages that having a wide range of application, the research to ultraviolet-curing paint in recent years and should
With increasing year by year.
Ultraviolet-curing paint is prepared usually using linear oligomer, and the reactive diluents that add are lived more with reducing viscosity
Property diluent adds the toxicity and pollution of coating.In recent years, dissaving polymer makes it due to its unique design feature
As the study frontier (Prog.Org.Coat.2014,77,94 of 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, effectively reduce volatile organic compounds
(VOC) discharge；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, causes unreacted functional group more than needed, unreacted labile functional groups can reduce the steady of paint film
Qualitative and patience, therefore Hyperbranched Polymer has some limitations.
The content of the invention
The present invention cures hyperbranched star polymer coating in view of the shortcomings of the prior art, providing a kind of ultraviolet light.The over-expense
Changing star polymer includes dissaving polymer kernel and linear polymer arm, can combine dissaving polymer and linear polymerization
The advantages of thing.Dissaving polymer kernel can reduce system viscosity, provide abundant functional group and branched structure, linear polymerization
Thing arm can reduce the crosslinking steric hindrance of system, improve the degree of cross linking of system, unreacted functional group be reduced, so as 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 constructs
A kind of hyperbranched star polymer, using for ultraviolet-curing paint.
The present invention provides a kind of ultraviolet light and cures hyperbranched star polymer coating, to solve linear polymerization in the prior art
Thing 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 method of the hyperbranched star polymer of above-mentioned uV curable.
The present invention also provides above-mentioned ultraviolet light cure the heat endurance 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 cures hyperbranched star polymer coating
Ring.
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
Compound kernel and linear polymer arm, the dissaving polymer kernel pass through chemical key connection with linear polymer arm；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 that the dissaving polymer kernel, which is core, its per molecule on average
Containing 64 hydroxyls, its theoretical molecular is 7214g/mol.
Preferably, the linear polymer arm is biodegradable polycaprolactone arm, its 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, its comprehensive performance is optimal.
Preferably, the method for the group that the terminal hydroxy group of the hyperbranched star polymer is modified to carbon-carbon double bonds is：Will
Hyperbranched star polymer and excessive blocking agent reaction, are blocked with methacrylic acid group, you can；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, bag
Include following steps：
(1) hyper-branched polyester and 6-caprolactone are subjected to ring-opening polymerization under catalyst a effects, obtain hyperbranched star
Shape polymer one；
(2) hyperbranched star polymer one carries out ester exchange reaction, dead-end polymerization with end-capping reagent under the action of catalyst b
Thing, 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 the end-capping reagent and the hyper-branched polyester institute hydroxyl described in 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 rate of charge is 1:20；Catalyst b described in step (2) is triethylamine and 4-dimethylaminopyridine, and the triethylamine is with overspending
The molar feed ratio for changing polyester institute hydroxyl is 3:1, mole of the 4-dimethylaminopyridine and hyper-branched polyester institute hydroxyl
Rate of charge is 1:2.5.
Preferably, the ring-opening polymerisation described in step (1) is polymerisation in bulk, the ester exchange reaction institute described in step (2)
It is dichloromethane with solvent.
Preferably, ring-opening polymerization temperature described in step (1) is 130 DEG C, when the reaction time is 5 small；In step (2)
The ester exchange reaction is to be reacted under ice bath, when the reaction time is 5 small.
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 purifies.
Preferably, the reaction products therefrom cold methanol through step (1)：Ether=1:1 mixed organic solvents into
Row precipitation, filters afterwards, 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 afterwards, and 35 DEG C of drying, obtain hyperbranched star
Shape polymer two.
The third aspect, the hyperbranched star polymer the present invention provides a kind of uV curable are preparing 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 field such as car and medical treatment.
Fourth aspect, the present invention provides a kind of preparation method of ultraviolet-curing paint, including can be purple using foregoing
The hyperbranched star polymer of outer photocuring is mixed with photoinitiator, to obtain the final product.
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 propiophenones, and dosage is 3% mass fraction.
Foregoing ultraviolet-curing paint 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, 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 cure hyperbranched star polymer coating, its 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 cures hyperbranched star polymer coating,
Its polycaprolactone arm improves the stability and patience of paint film.
Compared with prior art, the present invention has following beneficial effect：
1st, hyperbranched star polymer of the invention, due to the use of hyper-branched polyester inner core molecule between twined 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；
2nd, hyperbranched star polymer of the invention, as a kind of ultraviolet-curing paint, curing rate is fast, energy expenditure
Considerably less than heat drying, the application available for various thermo-sensitive materials；
3rd, ultraviolet light of the invention cures hyperbranched star polymer coating, including dissaving polymer kernel with can biology
The linear polymer arm of degraded, between the two by chemical key connection, with methacrylate to hyperbranched star polymer
Terminal hydroxy group the advantages of being modified, dissaving polymer and linear polymer can be combined.Dissaving polymer kernel can
The crosslinking steric hindrance of system can be reduced, carry by reducing system viscosity, the functional group that offer is enriched and branched structure, linear polymer arm
The degree of cross linking of high system, reduces unreacted functional group, so as 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；
4th, ultraviolet light of the invention cures 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, it in turn ensure that hardness, adhesive force and the patience of coating；
5th, 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 paint film property is improved；Cause
And ultraviolet light curing hyperbranched star polymer coating of the invention has higher cost performance, it is hopeful to be applied to actual
In industrial production.
Brief description of the drawings
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, further 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 spectras；
Fig. 3 is the grafting dissaving polymer H that embodiment 1 synthesizes40-star-PCL20's13C NMR spectras；
Fig. 4 is the methacrylate end-blocking grafting dissaving polymer H that embodiment 1 synthesizes40-star-PCL20- MAC's1H NMR spectras；
Fig. 5 is the methacrylate end-blocking grafting dissaving polymer H that embodiment 1 synthesizes40-star-PCL20-MAC
's13C NMR spectras；
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.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following embodiments will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, some changes and improvements can also be made.These belong to the present invention
Protection domain.
Hyperbranched star polymer in the present invention, including dissaving polymer kernel and biodegradable linear polymerization
Thing arm, modifies the terminal hydroxy group of hyperbranched star polymer with methacrylic anhydride.The hyperbranched star polymerization of the present invention
Thing, has quick-setting ability under ultraviolet light, in the case where the linear polymeric arms degree of polymerization is suitable, hyperbranched star polymerization
Thing combines the advantages of dissaving polymer and linear polymer, improves the levelability of coating, solidification rate, hardness, attachment
Power and patience etc..
It is intermolecular bright almost without chain entanglement, viscosity and the dissaving polymer is due to its unique three-dimensional spherical structure
The aobvious linear oligomer being less than with molecular weight；And global molecular surface has abundant functional group, therefore, the UV light
Change hyperbranched star polymer coating, its 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 cures hyperbranched star polymer coating, its 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, its comprehensive performance is optimal.
Compared with prior art, ultraviolet light of the present invention cures hyperbranched star polymer coating, breaches linear
The limitation of polymer coating and Hyperbranched Polymer, it is big, hyperbranched to solve linear polymer viscosity in the prior art
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 cures hyperbranched star polymer coating includes the following steps：
(1) it is grafted the preparation of dissaving polymer：
Exemplified by preparation method when the degree of polymerization of polycaprolactone is 20.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 bulb,
Under nitrogen atmosphere, H is made40It is dissolved completely in 6-caprolactone, is warming up to 130 DEG C, adds catalyst Sn (Oct)2, catalyst with
The molar feed ratio of hyper-branched polyester institute hydroxyl is 1:20, trigger ring-opening polymerization, stirring, when reaction 5 is small, obtains sticky
Liquid.After being cooled to room temperature, into reaction bulb plus tetrahydrofuran dissolves, in 400mL cold methanols/ether (1:1) precipitation in, filters
After obtain white solid particle, at 35 DEG C it is dry 24 it is small when, hyperbranched star polymer one is obtained, 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 prepare the degree of polymerization and (use four generation hyper-branched polyester H for 1540(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, labeled as H40-star-PCL15And H40-star-PCL25。
(2) methacrylate end-blocking grafting dissaving polymer：
Exemplified by preparation method when the degree of polymerization of polycaprolactone is 20.The H that will be prepared40-star-PCL20
(5.00g, hydroxyl containing 7.10mmol) is dissolved in 15mL dichloromethane, under nitrogen atmosphere, adds catalyst of triethylamine
(0.607g, 6.00mmol) and 4-dimethylaminopyridine (0.100g, 0.82mmol), triethylamine and hyper-branched polyester institute hydroxyl
Molar feed ratio be 3:The molar feed ratio of Isosorbide-5-Nitrae-dimethylamino naphthyridine and hyper-branched polyester institute hydroxyl is 1:2.5.Reaction
Dry ball of the access equipped with anhydrous calcium chloride, reacts and is carried out under ice bath on bottle.The methyl-prop in 3mL dichloromethane will be diluted in
Olefin(e) acid acid anhydride (0.617g, 4.00mmol) is added dropwise in reaction bulb, and stirring, when reaction 3 is small, obtains light yellow viscous liquid.To
Dichloromethane cut back is added in reaction bulb, is precipitated in 400mL cold methanols, is filtered, with being obtained after cold milli-Q water 3 times
White solid particle, when drying 24 is small at 35 DEG C, obtains hyperbranched star polymer two, labeled as H40-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, mark
For H40-star-PCL15- MAC and H40-star-PCL25-MAC。
In addition, in order to the characteristics of embodying g-polycaprolactone arm and be contrasted, H is equally synthesized40- MAC, i.e., directly use 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 fraction (exemplified by 10%) such as：
Take H40-star-PCLn(0.5g) is dissolved in 3mL dichloromethane, add the photoinitiator 2- hydroxyls of 3% mass fraction-
2- methyl phenyl ketones, tinplate sheet by cleaning treatment is applied to the spreading rods of 30 μ m-thicks by solution, be placed on power 300W,
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 waiting mass fraction, 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 dichloromethane, add the photoinitiator 2- hydroxyls of 3% mass fraction-
2- methyl phenyl ketones, tinplate sheet by cleaning treatment is applied to the spreading rods of 30 μ m-thicks by solution, be placed on power 300W,
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 of equimolar concentration, the content of hyper-branched polyester is identical in system, differs only in 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, it is 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, by the integral area for comparing the above two signal peaks, you can obtain averagely every
A H40The number of contained polycaprolactone arm, then the ratio of both signal peak integral areas is H40-star-PCLnThe degree of polymerization,
The results show calculates the degree of polymerization and is approached with the theoretical degree of polymerization.
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 tests.About 7mg samples are weighed, are 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 is warming up to 150 DEG C, heating speed
Rate and rate of temperature fall are 10 DEG C/min.H40-star-PCL20DSC test curves as shown in fig. 6, the crystallization of all samples
Degree, melting origin temp, fusing point, glass transition temperature TgIt is listed in table 2.Since polycaprolactone is a kind of hemicrystalline polymerization
Thing, therefore with the increase of the polycaprolactone degree of polymerization, the crystallinity increase of hyperbranched star polymer, with 166.5J/g during calculating
Melting heat as 100% crystallinity；The fusing point of polycaprolactone is 60~63 DEG C, TgFor -60 DEG C, with the increasing of polycaprolactone arm
It is long, molecular weight increase, the flexible raising of hyperbranched star polymer, therefore fusing point increase, TgReduce；Methacrylic acid anhydride modification
Hyperbranched star polymer, branch terminals introduce ester group, and end group polarity declines, and the soft segment increase in molecule, thus Tg
Decline.
Table 2
| Sample | Crystallinity (%) | Melt 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 tests.Sample quality about 5mg, in nitrogen atmosphere
Under, 600 DEG C are heated to from 50 DEG C with the speed of 20 DEG C/min, the heat endurance of determination 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 heat endurance.G-polycaprolactone arm, hyperbranched star polymer
Heat decomposition curve shows as two sections, i.e. two sections of polycaprolactone and hyper-branched polyester, the successful grafting of side illustration polycaprolactone arm；
With methacrylic anhydride to hyperbranched star polymer end hydroxyl modification after, heat decomposition temperature has obvious raising, be because
The methacrylate of modified end group has the function of crosslinking, is crosslinked in thermal histories, and global molecular will be easier to decompose
Ester bond parcel in the molecule, therefore, heat endurance 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 cures, and carries out performance to paint film
Test, it is 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 waiting mass fraction, 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.With the coating rod coating 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 hardening time point
Analysis, test result are listed in table 4.Determination of Hardness method refers to GB/T6739-2006, and adhesive force assay method refers to GB/T 1720-
79, resistance to acid and alkali assay 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 in the case where waiting mass fraction, polycaprolactone arm is shorter, over-expense
Change the methyl that the relative amount of polyester is higher, and the viscosity of system is lower, and the functional group content in system is higher, has the function of crosslinking
Acrylate end groups are more, thus crosslink density is bigger, and the C=C double bonds of hyper-branched polyester are mainly distributed on global molecular
Surface, when carrying out ultraviolet light curing, 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 curing speed more than dissaving structure content
Rate performance is more preferable.But at the same time 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 more than between linear molecule
Crosslinking steric hindrance, cause to contain unreacted C=C double bonds more than needed in paint film, reduce the acid resistance and alkali resistance of paint film.This reality
Apply the advantages of the paint film property test experiments of example have fully demonstrated dissaving structure and shortcoming.
Table 4
" levelability, acid resistance, alkali resistance " is optimal with 10 in table 4, and numerical value is smaller to represent that performance 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 of equimolar concentration, the content of hyper-branched polyester is identical in system, differs only in poly-
The length of caprolactone arm, it is thus possible to the characteristics of embodying g-polycaprolactone arm.With the coating rod coating of 30 μ m-thicks, due to matter
It is different to measure fraction, film thickness differs, 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
Thing paint film equally carries out hardness, adhesive force, acid resistance, alkali resistance, levelability and the test analysis of hardening time, test result row
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 curing speed of paint film
Degree performance is better, this is because in the case of equimolar concentration, the hyperbranched poly ester content in system is identical, thus functional group
Content is identical, and with the growth of polycaprolactone arm, the mass fraction increase of system, solvent content is reduced, while soft segment increases
Add, greatly reduce crosslinking steric hindrance, when carrying out ultraviolet light curing, polycaprolactone arm improves the degree of cross linking of reaction, improves
The density of cross-linked network structure, effectively reduces unreacted C=C double bonds 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 at the same time 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 shortcoming.
Table 5
" levelability, acid resistance, alkali resistance " is optimal with 10 in table 5, and numerical value is smaller to represent that performance is poorer.
It is in table 5 the results show that three kinds of hyperbranched star polymer coatings and H produced by the present invention40Compare, it is hardness, attached
Put forth effort, resistance to acid and alkali has lifting.Illustrate to be prepared into after hub-and-spoke configuration, main advantage is that crosslinking when reducing curing
Steric hindrance, improves cross-linking reaction degree, reduces unnecessary functional group, so as to improve performance.
H is shown in table 440Performance it is more excellent, be due to the hyperbranched poly in four groups of samples in the case where waiting mass fraction
Ester content difference is excessive, and variable is not unique, therefore the characteristics of major embodiment hyper-branched polyester, it is difficult to the characteristics of embodying PCL arms.
Therefore, in table 5, we control H in sample40Content it is identical, the characteristics of to embody PCL arms.
Four kinds of paint films in the present embodiment are each advantageous, are hopeful to be applied in different fields.For Integrated comparative, when
When the degree of polymerization of polycaprolactone is 20, H40-star-PCL20Paint film made-MAC 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 paint film property is improved；This hair
Bright hyperbranched star polymer coating effectively reduces the dosage of reactive diluent and solvent, can effectively reduce the discharge of VOC；
Thus, ultraviolet light of the invention, which cures hyperbranched star polymer coating, has higher cost performance, is hopeful to be applied to reality
Industrial production in.
Offer one kind ultraviolet light that the present invention innovates cures hyperbranched star polymer coating, dissaving polymer kernel with
Linear polymer arm is modified the terminal hydroxy group of hyperbranched star polymer with methacrylic anhydride by chemical key connection,
Assign its ultraviolet light and cure function.The characteristics of present invention combines dissaving polymer and linear polymer coating, utilization is hyperbranched
Polymer low viscosity, functional group are enriched and the advantage of spherical branched structure, and utilizes the flexible height of linear polymer and crosslinking steric hindrance
Small advantage, be prepared for can rapid curing under ultraviolet light, and with preferable levelability, hardness, solidification rate, adhesive force, resistance to
The performance hyperbranched star polymer coatings such as acid and alkali resistance, and the degree of polymerization of linear polymer has been probed into coating property
Influence.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 above-described embodiment, 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.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or change within the scope of the claims, this not shadow
Ring the substantive content of the present invention.In the case where there is no conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (10)
1. the hyperbranched star polymer of a kind of uV curable, it is characterised in that including dissaving polymer kernel and line
Property polymeric arms, the dissaving polymer kernel and linear polymer arm pass through chemical key connection；The hyperbranched star gathers
The terminal hydroxy group of compound is modified to the group of carbon-carbon double bonds.
2. the hyperbranched star polymer of uV curable as claimed in claim 1, it is characterised in that the hyperbranched poly
Compound kernel is hyper-branched polyester kernel.
3. the hyperbranched star polymer of uV curable as claimed in claim 1, it is characterised in that the linear polymerization
Thing arm is biodegradable polycaprolactone arm, its degree of polymerization is 15~25.
4. the hyperbranched star polymer of uV curable as claimed in claim 1, it is characterised 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 is：By hyperbranched star polymer and excessive end-blocking
Agent is reacted, you can；The end-capping reagent is methacrylic anhydride.
5. a kind of preparation method of the hyperbranched star polymer of the uV curable as described in any in 1-4 such as claim,
It is characterised in that it includes following steps：
(1) hyper-branched polyester and 6-caprolactone are subjected to ring-opening polymerization under catalyst a effects, obtain hyperbranched star and gather
Compound one；
(2) hyperbranched star polymer one and end-capping reagent carry out ester exchange reaction under the action of catalyst b, terminated polymer,
The hyperbranched star polymer two that end group is carbon-carbon double bonds group is obtained, i.e. the cured hyperbranched star of ultraviolet light gathers
Compound.
6. the preparation method of the hyperbranched star polymer of uV curable as claimed in claim 5, it is characterised 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 the end-capping reagent and the hyper-branched polyester institute hydroxyl described in step (1) is 2:1.
7. the preparation method of the hyperbranched star polymer of uV curable as claimed in claim 5, it is characterised 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 rate of charge is 3:1, 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 polymerisation in bulk, and the ester exchange reaction solvent for use described in step (2) is dichloro
Methane.
8. the preparation method of the hyperbranched star polymer of uV curable as claimed in claim 5, it is characterised in that step
Suddenly ring-opening polymerization temperature described in (1) is 130 DEG C, when the reaction time is 5 small；Ester exchange reaction is described in step (2)
Reacted under ice bath, when the reaction time is 5 small.
9. a kind of hyperbranched star polymer of uV curable as claimed in claim 1 is preparing ultraviolet-curing paint
In application.
10. a kind of preparation method of ultraviolet-curing paint, it is characterised in that including using described in claim any one of 1-4
The hyperbranched star polymer of uV curable mixed with photoinitiator, to obtain the final product；
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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711231344.3A CN108003337B (en) | 2017-11-29 | 2017-11-29 | Hyperbranched star polymer of uV curable and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711231344.3A CN108003337B (en) | 2017-11-29 | 2017-11-29 | Hyperbranched star polymer of uV curable and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108003337A true CN108003337A (en) | 2018-05-08 |
| CN108003337B CN108003337B (en) | 2019-10-08 |
Family
ID=62054934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711231344.3A Active CN108003337B (en) | 2017-11-29 | 2017-11-29 | Hyperbranched star polymer of uV curable and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108003337B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105553A (en) * | 2019-04-04 | 2019-08-09 | 湖南师范大学 | Ester modified itaconic acid base water borne UV curing resin of hyperbranched poly and preparation method thereof |
| CN115787132A (en) * | 2022-09-15 | 2023-03-14 | 江苏恒力化纤股份有限公司 | Preparation method of creep-resistant polyester industrial yarn |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911349A (en) * | 2012-10-11 | 2013-02-06 | 华南理工大学 | Caprolactone modified hyperbranched polyester and preparation method and application thereof |
-
2017
- 2017-11-29 CN CN201711231344.3A patent/CN108003337B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911349A (en) * | 2012-10-11 | 2013-02-06 | 华南理工大学 | Caprolactone modified hyperbranched polyester and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 施文芳: "星形超支化聚酯的合成及其光固化", 《感光科学与光化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105553A (en) * | 2019-04-04 | 2019-08-09 | 湖南师范大学 | Ester modified itaconic acid base water borne UV curing resin of hyperbranched poly and preparation method thereof |
| CN115787132A (en) * | 2022-09-15 | 2023-03-14 | 江苏恒力化纤股份有限公司 | Preparation method of creep-resistant polyester industrial yarn |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108003337B (en) | 2019-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sangermano et al. | Preparation and characterization of hybrid thiol‐ene/epoxy UV–thermal dual‐cured systems | |
| Qiu et al. | Preparation, characterization and properties of UV-curable waterborne polyurethane acrylate/SiO 2 coating | |
| Brännström et al. | Biobased UV-curable coatings based on itaconic acid | |
| CN108003337B (en) | Hyperbranched star polymer of uV curable and its preparation method and application | |
| Yin et al. | Synthesis, photopolymerization kinetics, and thermal properties of UV-curable waterborne hyperbranched polyurethane acrylate dispersions | |
| PT779908E (en) | CURRENT RADIATION RESINS UNDERSTANDING HYPER-RAMPED POLYESTERS | |
| Nilsson et al. | Synthesis and thiol–ene photopolymerization of allyl‐ether functionalized dendrimers | |
| Wang et al. | Synthesis and properties of UV-curable polyester acrylate resins from biodegradable poly (l-lactide) and poly (ε-caprolactone) | |
| Trey et al. | Thiol–ene networks and reactive surfaces via photoinduced polymerization of allyl ether functional hyperbranched polymers | |
| Zhang et al. | Photopolymerization behavior and properties of highly branched poly (thioether-urethane) acrylates used for UV-curing coatings | |
| Li et al. | One-step synthesis of novel multifunctional silicone acrylate prepolymers for use in UV-curable coatings | |
| Li et al. | Preparation and properties of castor oil-based dual cross-linked polymer networks with polyurethane and polyoxazolidinone structures | |
| Li et al. | Synthesis and properties of a low-viscosity UV-curable oligomer for three-dimensional printing | |
| Li et al. | High toughness induced by wormlike-nanostructure in epoxy thermoset containing amphiphilic PDMS–PCL block copolymers | |
| Zheng et al. | Design of robust superhydrophobic coatings using a novel fluorinated polysiloxane with UV/moisture dual cure system | |
| Keramatinia et al. | Synthesis and viscoelastic properties of acrylated hyperbranched polyamidoamine UV-curable coatings with variable microstructures | |
| Zhang et al. | Preparation of novel UV-cured methacrylate hybrid materials with high thermal stability via thiol–ene photopolymerization | |
| Zhang et al. | UV curable soybean‐oil hybrid systems based on thiol‐acrylate and thiol‐ene‐acrylate chemistry | |
| Li et al. | Preparation of multifunctional silicone acrylate prepolymers with anti-oxygen inhibition ability for application in UV-curable anti-smudge coatings | |
| Zhang et al. | Mussel-inspired polymer: a photocurable and degradable polymer network for adhesives | |
| Kong et al. | Tannic acid as a natural crosslinker for catalyst-free silicone elastomers from hydrogen bonding to covalent bonding | |
| Zhang et al. | Study on reactive polydimethylsiloxane-modified waterborne polyurethanes | |
| Remeikyte et al. | Synthesis and properties of photocross‐linked polymers of epoxidized linseed oil with different reactive diluents | |
| Pezzana et al. | Sustainable approach for coating production: Room temperature curing of diglycidyl furfuryl amine and itaconic acid with UV-induced thiol-ene surface post-functionalization | |
| Liu et al. | Synthesis of a novel hyperbranched polyester with carboxyl end groups applied to UV-curable waterborne coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |