Embodiment
The invention provides a kind of polyaryletherketone with formula (I) structure:
Wherein, R is H or methyl; 1≤m≤4; N is the polymerization degree.
Polyaryletherketone provided by the invention has formula (I) structure, and wherein, R is H or methyl, is preferably H; 1≤m≤4, m is preferably 2 or 3; N is the polymerization degree, preferred 1≤n≤500, more preferably 2≤n≤200, most preferably 3≤n≤100.
The present invention is grafted to the propenyl ester group on the side chain of phenolphthalein polyaryletherketone, the polyaryletherketone of (I) structure that obtains having formula, and it has more cross-linking set and good resistance toheat, can be used as products such as high temperature resistant type ultraviolet-curing paint.
In the present invention, said color with polyaryletherketone of formula (I) structure is white;
Said limiting viscosity >=0.05dL/g with polyaryletherketone of formula (I) structure;
Said second-order transition temperature with polyaryletherketone of formula (I) structure is 140 ℃~265 ℃;
The temperature of the initial weightlessness of said polyaryletherketone with formula (I) structure is 300 ℃~385 ℃, and weightless 5% temperature is 400 ℃~490 ℃.
The present invention also provides a kind of preparation method of polyaryletherketone, comprising:
In the presence of dewatering agent and catalyzer, the polyaryletherketone that will have formula (II) structure carries out esterification with the propenoate with formula (III) structure in organic solvent, the polyaryletherketone of (I) structure that obtains having formula;
Wherein, R is H or methyl; 1≤m≤4; N is the polymerization degree.
The present invention is preferably under rare gas element such as nitrogen protection; To have the polyaryletherketone of formula (II) structure, propenoate, dewatering agent, catalyzer and organic solvent and add in the reactor drum polyaryletherketone that obtains having formula (I) structure after the esterification with formula (III) structure.
The present invention is a raw material with the polyaryletherketone with formula (II) structure; Contain carboxyl on the side chain of said polyaryletherketone with formula (II) structure; The similar molecular of overall molecular structure and phenolphthalein polyaryletherketone; Can abbreviate PEK-L as, therefore, the polyaryletherketone that said polyaryletherketone with formula (II) structure can be (I) structure that has formula provides the characteristic of phenolphthalein polyaryletherketone.
The present invention does not have particular restriction to the said polymerization degree (n) with polyaryletherketone of formula (II) structure, preferred 1≤n≤500, more preferably 2≤n≤200, most preferably 3≤n≤100;
The present invention does not have particular restriction to said source with polyaryletherketone of formula (II) structure, preferably prepares according to following preparation method:
In the presence of basic cpd and band aqua, with phenolphthalin and 4,4 '-the dihalo-benzophenone reacts in organic solvent, the polyaryletherketone of (II) structure that obtains having formula.
The preparation method of said polyaryletherketone with formula (II) structure is preferably under rare gas element such as nitrogen protection; With phenolphthalin, 4; 4 '-dihalo-benzophenone, basic cpd, band aqua and organic solvent add in the reactor drum polyaryletherketone that obtains having formula (II) structure after the reaction.
In the preparation method of said polyaryletherketone with formula (II) structure, said phenolphthalin abbreviates PPL as; Said 4,4 '-the dihalo-benzophenone is preferably 4,4 '-difluoro benzophenone or 4,4 '-two chloro benzophenones, more preferably 4,4 '-difluoro benzophenone; Said phenolphthalin and said 4,4 '-mol ratio of dihalo-benzophenone is preferably (1~3): 1, more preferably (1~2.5): 1, most preferably be 1: 1;
Said basic cpd can be to having reacted katalysis, and said basic cpd is preferably Anhydrous potassium carbonate (K
2CO
3) or soda ash light (Na
2CO
3), Anhydrous potassium carbonate more preferably; The mol ratio of said basic cpd and said phenolphthalin is preferably (1~3): 1, more preferably (1.1~2.5): 1, most preferably be (1.15~2): 1;
Said organic solvent is the medium of reaction, and said organic solvent is preferably DMSO 99.8MIN. or THF, more preferably DMSO 99.8MIN.; The consumption of said organic solvent adopts the consoluet consumption of above-mentioned raw materials is got final product;
Said band aqua can be separated the water that reaction produces from reaction system, thereby improves reaction efficiency, and said band aqua is preferably YLENE or toluene, more preferably toluene; The volume ratio of said organic solvent and said band aqua is preferably 1: (1~3), more preferably 1: (1.5~2.5) most preferably are 1: (1.8~2).
The preparing method's of said polyaryletherketone with formula (II) structure reaction formula is preferably suc as formula shown in (1):
Said preparation method with polyaryletherketone of formula (II) structure preferably is specially:
In the presence of basic cpd and band aqua, with phenolphthalin and 4,4 '-the dihalo-benzophenone carries out the first step reaction, obtains intermediate product in organic solvent;
Said intermediate product is carried out the second step reaction, the polyaryletherketone of (II) structure that obtains having formula.
Wherein, said the first step reaction is main with nucleophilic substitution reaction, and the temperature of said the first step reaction is preferably 130 ℃~150 ℃, more preferably 135 ℃~145 ℃; The time of said the first step reaction is preferably 1h~3h, more preferably 1.5h~2.5h;
Said band aqua is taken the water that reaction produces out of, preferably steam whole said band aquas after, obtain intermediate product, said intermediate product comprises product and the small amounts of oligomer of nucleophilic substitution reaction etc.;
Said second step reaction is main with polycondensation, and the temperature of said second step reaction is preferably 170 ℃~180 ℃; The time of said second step reaction is preferably 3h~5h, more preferably 3.5h~4.5h.
When reaction obtains yellow thick polymer product; With N (DMF) dilution and static layering; The supernatant liquid that then static layering is obtained is slowly poured in the mixing sinking agent that is made into by ethanol and hydrochloric acid; Separate out a large amount of white masses, it is boiled to wash repeatedly be placed in the vacuum drying oven dryly, obtain polyaryletherketone white, that have formula (II) structure.
Gained limiting viscosity white, that have the polyaryletherketone of formula (II) structure is 0.29dL/g, and second-order transition temperature is 191 ℃, and the temperature of initial weightlessness is 391 ℃, and weightless 5% temperature is 403 ℃.
In the preparation method of above-mentioned polyaryletherketone with formula (II) structure, phenolphthalin is one of raw material, and said phenolphthalin can be buied from market, also can prepare according to following preparation method:
With the zinc powder is catalyzer; With reacting after phenolphthalein (ph), sodium hydroxide, deionized water and the ethanol mixing; Preferred 11h~13h, more preferably pour in the hydrochloric acid acidifying and filtering behind 11.5h~12.5h into, the crude product that filtration is obtained boils repeatedly with deionized water and refilters after washing, drying, obtains phenolphthalin; Productive rate is more than 95%, and reaction formula is suc as formula shown in (2):
In the preparation method of the polyaryletherketone with formula (I) structure provided by the invention; The propenoate of another raw material for having formula (III) structure; Contain reactive groups such as two keys in the molecular structure of said propenoate with formula (III) structure, it provides the cross-linking set that can carry out crosslinking reaction for the polyaryletherketone with formula (I) structure.
Said propenoate with formula (III) structure is preferably Rocryl 400, Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 410 or vinylformic acid-4-hydroxyl butyl ester.In the present invention; Change polyaryletherketone and said mol ratio with propenoate of formula (III) structure with formula (II) structure; Can obtain the esterification products of a series of different percentage of grafting, the present invention does not have particular restriction to said polyaryletherketone and said mol ratio with propenoate of formula (III) structure with formula (II) structure, is preferably 1: 1~10: 1; More preferably 2: 1~8: 1, most preferably be 4: 1~6: 1.
In the preparation method of the polyaryletherketone with formula (I) structure provided by the invention, said dewatering agent is beneficial to reaction to carry out, and can improve reaction efficiency; Said dewatering agent is preferably N, N '-NSC 57182 (DCC), N, N '-DIC (DIC) or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC), N more preferably, N '-NSC 57182; Said dewatering agent and said mol ratio with propenoate of formula (III) structure are preferably (0.1~5): 1, more preferably (1~4): 1, most preferably be (1~1.5): 1.
Said catalyzer is this area catalyzer commonly used, is preferably 4-Dimethylamino pyridine (DMAP), and it has katalysis efficiently; The mol ratio of said catalyzer and said dewatering agent is preferably (0.1~1): 1, more preferably (0.8~1): 1.
Said organic solvent is this area organic solvent commonly used, is preferably DMSO 99.8MIN. (DMSO) or THF (THF), more preferably DMSO 99.8MIN.; The quality of said polyaryletherketone with formula (II) structure is preferably (0.1~1) g: 1mL with the ratio of said volume of organic solvent, more preferably (0.5~0.8) g: 1mL.
The propenoate that the present invention will have the polyaryletherketone (PEK-L) of formula (II) structure and have formula (III) structure carries out esterification under the effect of dewatering agent and catalyzer; Obtain esterification products; The polyaryletherketone that promptly has formula (I) structure, reaction formula are preferably suc as formula shown in (3):
Wherein, the temperature of said esterification is preferably 10 ℃~40 ℃, more preferably 20 ℃~30 ℃; The time of said esterification is preferably 12h~48h, and more preferably 15h~40h most preferably is 20h~30h.The preparation method of the polyaryletherketone with formula (I) structure provided by the invention is simple to operate, and reaction conditions is gentle, and productive rate is higher, is suitable for suitability for industrialized production.
Esterification obtains suspension liquid after finishing, and pours in the mixing solutions that is made into by ethanol and hydrochloric acid after the present invention filters it and precipitates; To remove residual impurity such as dewatering agent; To precipitate the gained material then and boil repeatedly and wash, and place vacuum drying oven dry again, obtain white cotton-shaped product.
After obtaining white cotton-shaped product, it is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy.Analytical results shows, the polyaryletherketone of the cotton-shaped product of said white for having formula (I) structure.
Said polyaryletherketone with formula (I) structure is dissolved among the DMF at 25 ℃, measures its limiting viscosity.Mensuration result shows, said limiting viscosity >=0.05dL/g with polyaryletherketone of formula (I) structure.
Utilize METTLER TOLEDO DSC1 DSC to measure said second-order transition temperature with polyaryletherketone of formula (I) structure, condition determination is following: under nitrogen protection, heat-up rate is 10 ℃/min, and the TR of mensuration is 0 ℃~300 ℃.Mensuration result shows that said second-order transition temperature with polyaryletherketone of formula (I) structure is 140 ℃~265 ℃.
Utilize METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer to measure said thermal decomposition performance with polyaryletherketone of formula (I) structure, condition determination is following: under nitrogen protection, heat-up rate is 10 ℃/min, and the TR of mensuration is 0 ℃~550 ℃.Mensuration result shows, the temperature of the initial weightlessness of said polyaryletherketone with formula (I) structure is 300 ℃~385 ℃, and weightless 5% temperature is 400 ℃~490 ℃.
Experimental result shows; Polyaryletherketone with formula (I) structure provided by the invention has the characteristic of propenyl ester group and phenolphthalein polyaryletherketone simultaneously; Promptly have more cross-linking set and good resistance toheat, can be used as products such as high temperature resistant type ultraviolet-curing paint.
In order to further specify the present invention, polyaryletherketone provided by the invention and preparation method thereof is described particularly below in conjunction with embodiment.
Embodiment 1
In the there-necked flask of 100mL, add 12.81g (0.04mol) phenolphthalin, 8.73g (0.04mol) 4,4 '-difluoro benzophenone, 11.06g (0.08mol) K successively
2CO
3, 34mLDMSO and 38mL toluene, feed nitrogen and stir, be warming up to 140 ℃ and react, dewater behind the reaction 2h; Steam whole toluene, slowly be warming up to 175 ℃ then, behind the isothermal reaction 4h; The yellow thick product that reaction is obtained with DMF dilution, static layering after, the supernatant liquid that obtains is slowly poured in the mixed solvent that is made into by ethanol and hydrochloric acid, separate out a large amount of white masses; It is boiled to wash repeatedly be placed in the vacuum drying oven dryly, obtain white product PEK-L, productive rate is 88%.
Embodiment 2
PEK-L, 0.11g (1mmol) Hydroxyethyl acrylate, 0.21g (1mmol) DCC, 0.01g (0.1mmol) DMAP and the 10mLDMSO of 0.53g (1mmol) embodiment 1 preparation placed the there-necked flask of 100mL; Logical nitrogen also stirs; Under 25 ℃ temperature, carry out esterification, obtain flaxen suspension liquid behind the 24h, under vigorous stirring, slowly pour in the mixing solutions that is made into by ethanol and hydrochloric acid after it is filtered and precipitate; To remove residual DCC and the NSC 30023 among the DCC (DCU); To precipitate the gained material and boil repeatedly and wash, and place vacuum drying oven dry again, obtain white product; Promptly have the polyaryletherketone (PEK-LH) of formula (IV) structure, productive rate is 79%.
The gained white product is carried out nuclear magnetic resonance spectroscopy, and analytical results is referring to Fig. 1, the hydrogen nuclear magnetic resonance spectrogram of the polyaryletherketone with formula (IV) structure that Fig. 1 obtains for the embodiment of the invention 2.Can know by Fig. 1; At the peak of 3.3081ppm chemical shift place is the absorption peak of water impurity; At the peak of 2.5008ppm chemical shift place is the absorption peak of solvent DMSO; At the peak of 7.7337ppm chemical shift place is the absorption peak of 14 hydrogen on the benzophenone phenyl ring; Being 7 the absorption peak of hydrogen on the side-chain benzene ring at the peak of 7.5099ppm chemical shift place, is 5 the absorption peak of hydrogen on the side-chain benzene ring at the peak of 7.3566ppm chemical shift place, is 6 the absorption peak of hydrogen on the side-chain benzene ring at the peak of 7.2019ppm chemical shift place; It at the peak of 7.0738ppm chemical shift place 1,2,4,13 the absorption peak of hydrogen on the benzophenone phenyl ring; Be 3 the absorption peak of hydrogen on the main chain at the peak of 6.4310ppm chemical shift place, 6.2954 with the peak of 6.2524ppm chemical shift place be 12 the absorption peak of hydrogen on the pendant double bonds, be 10 the absorption peak of hydrogen on the pendant double bonds at the peak of 6.1193ppm chemical shift place; Being 11 the absorption peak of hydrogen on the pendant double bonds at the peak of 5.8800ppm chemical shift place, is the absorption peak of the hydrogen of 8,9 of side chains at the peak of 4.3554ppm chemical shift place.
The gained white product is carried out IR spectroscopy, and analytical results is referring to Fig. 2, the infrared spectrogram of the polyaryletherketone with formula (IV) structure that Fig. 2 obtains for the embodiment of the invention 2.Can know by Fig. 2, at wave number 2942cm
-1The place on the phenyl ring=C-H stretching vibration characteristic peak, at wave number 1597cm
-1And wave number 1493cm
-1The place is the C=C stretching vibration absorption peak of phenyl ring, at wave number 1239cm
-1With wave number 1162cm
-1The place is respectively Ar-O-Ar key asymmetrical stretching vibration absorption peak and symmetrical stretching vibration absorption peak, at wave number 767cm
-1The place explains and contains aromatic ring frame in the polymer architecture for the hydrocarbon formation vibration on the substituted phenyl ring in ortho position; At wave number 3076cm
-1The place in the alkene=the stretching vibration characteristic peak of C-H, at wave number 1660cm
-1The place is for the stretching vibration characteristic peak of the two keys of C=C in the alkene, at wave number 922cm
-1With wave number 858cm
-1The place in the alkene=formation vibration of C-H, explain and contains pair keys in the polymer architecture; At wave number 2852cm
-1The place is the stretching vibration characteristic peak of alkyl C-H.
In sum, the polyaryletherketone of gained white product for having formula (IV) structure:
Measure gained according to method mentioned above and have the limiting viscosity of the polyaryletherketone of formula (IV) structure, the result shows that its limiting viscosity is 0.29dL/g;
Measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (IV) structure according to method mentioned above respectively; The result shows respectively; Its second-order transition temperature is 170 ℃, and the temperature of initial weightlessness is 421 ℃, and weightless 5% temperature is 424 ℃.
Embodiment 3
PEK-L, 0.13g (1mmol) Rocryl 400,0.21g (1mmol) DCC, 0.01g (0.1mmol) DMAP and the 10mLDMSO of 1.05g (2mmol) embodiment 1 preparation placed the there-necked flask of 100mL, and esterification is carried out in logical nitrogen and stirring under 25 ℃ temperature; Obtain flaxen suspension liquid behind the 24h; It is filtered the back under vigorous stirring, slowly pour in the mixing solutions that is made into by ethanol and hydrochloric acid and precipitate,, will precipitate the gained material and boil repeatedly and wash to remove residual DCC and DCU; Place vacuum drying oven dry again; Obtain white product, promptly have the polyaryletherketone of formula (I) structure, productive rate is 76%.
After obtaining white product, it is carried out nuclear magnetic resonance spectroscopy and IR spectroscopy, analytical results shows, the polyaryletherketone of gained white product for having formula (I) structure.
Measure gained according to method mentioned above and have the limiting viscosity of the polyaryletherketone of formula (I) structure, the result shows that its limiting viscosity is 0.29dL/g;
Measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure according to method mentioned above respectively; The result shows respectively; Its second-order transition temperature is 150 ℃, and the temperature of initial weightlessness is 336 ℃, and weightless 5% temperature is 419 ℃.
Embodiment 4
PEK-L, 0.13g (1mmol) Propylene glycol monoacrylate, 0.21g (1mmol) DCC, 0.01g (0.1mmol) DMAP and the 10mLDMSO of 1.58g (3mmol) embodiment 1 preparation placed the there-necked flask of 100mL, and esterification is carried out in logical nitrogen and stirring under 25 ℃ temperature; Obtain flaxen suspension liquid behind the 24h; It is filtered the back under vigorous stirring, slowly pour in the mixing solutions that is made into by ethanol and hydrochloric acid and precipitate,, will precipitate the gained material and boil repeatedly and wash to remove residual DCC and DCU; Place vacuum drying oven dry again; Obtain white product, promptly have the polyaryletherketone of formula (I) structure, productive rate is 73%.
After obtaining white product, it is carried out nuclear magnetic resonance spectroscopy and IR spectroscopy, analytical results shows, the polyaryletherketone of gained white product for having formula (I) structure.
Measure gained according to method mentioned above and have the limiting viscosity of the polyaryletherketone of formula (I) structure, the result shows that its limiting viscosity is 0.29dL/g;
Measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure according to method mentioned above respectively; The result shows respectively; Its second-order transition temperature is 152 ℃, and the temperature of initial weightlessness is 340 ℃, and weightless 5% temperature is 410 ℃.
Embodiment 5
PEK-L, 0.14g (1mmol) Rocryl 410,0.21g (1mmol) DCC, 0.01g (0.1mmol) DMAP and the 10mLDMSO of 1.58g (3mmol) embodiment 1 preparation placed the there-necked flask of 100mL, and esterification is carried out in logical nitrogen and stirring under 25 ℃ temperature; Obtain flaxen suspension liquid behind the 24h; It is filtered the back under vigorous stirring, slowly pour in the mixing solutions that is made into by ethanol and hydrochloric acid and precipitate,, will precipitate the gained material and boil repeatedly and wash to remove residual DCC and DCU; Place vacuum drying oven dry again; Obtain white product, promptly have the polyaryletherketone of formula (I) structure, productive rate is 70%.
After obtaining white product, it is carried out nuclear magnetic resonance spectroscopy and IR spectroscopy, analytical results shows, the polyaryletherketone of gained white product for having formula (I) structure.
Measure gained according to method mentioned above and have the limiting viscosity of the polyaryletherketone of formula (I) structure, the result shows that its limiting viscosity is 0.29dL/g;
Measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure according to method mentioned above respectively; The result shows respectively; Its second-order transition temperature is 159 ℃, and the temperature of initial weightlessness is 312 ℃, and weightless 5% temperature is 410 ℃.
Embodiment 6
PEK-L, 0.28g (2mmol) vinylformic acid-4-hydroxyl butyl ester, 0.42g (2mmol) DCC, 0.02g (0.2mmol) DMAP and the 10mLDMSO of 2.63g (5mmol) embodiment 1 preparation placed the there-necked flask of 100mL, and esterification is carried out in logical nitrogen and stirring under 25 ℃ temperature; Obtain flaxen suspension liquid behind the 24h; It is filtered the back under vigorous stirring, slowly pour in the mixing solutions that is made into by ethanol and hydrochloric acid and precipitate,, will precipitate the gained material and boil repeatedly and wash to remove residual DCC and DCU; Place vacuum drying oven dry again; Obtain white product, promptly have the polyaryletherketone of formula (I) structure, productive rate is 69%.
After obtaining white product, it is carried out nuclear magnetic resonance spectroscopy and IR spectroscopy, analytical results shows, the polyaryletherketone of gained white product for having formula (I) structure.
Measure gained according to method mentioned above and have the limiting viscosity of the polyaryletherketone of formula (I) structure, the result shows that its limiting viscosity is 0.29dL/g;
Measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure according to method mentioned above respectively; The result shows respectively; Its second-order transition temperature is 149 ℃, and the temperature of initial weightlessness is 323 ℃, and weightless 5% temperature is 420 ℃.
Embodiment 7
PEK-L, 0.22g (2mmol) Hydroxyethyl acrylate, 0.42g (2mmol) DCC, 0.02g (0.2mmol) DMAP and the 10mLDMSO of 4.20g (8mmo1) embodiment 1 preparation placed the there-necked flask of 100mL, and esterification is carried out in logical nitrogen and stirring under 25 ℃ temperature; Obtain flaxen suspension liquid behind the 24h; It is filtered the back under vigorous stirring, slowly pour in the mixing solutions that is made into by ethanol and hydrochloric acid and precipitate,, will precipitate the gained material and boil repeatedly and wash to remove residual DCC and DCU; Place vacuum drying oven dry again; Obtain white product, promptly have the polyaryletherketone of formula (I) structure, productive rate is 66%.
After obtaining white product, it is carried out nuclear magnetic resonance spectroscopy and IR spectroscopy, analytical results shows, the polyaryletherketone of gained white product for having formula (I) structure.
Measure gained according to method mentioned above and have the limiting viscosity of the polyaryletherketone of formula (I) structure, the result shows that its limiting viscosity is 0.29dL/g;
Measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure according to method mentioned above respectively; The result shows respectively; Its second-order transition temperature is 147 ℃, and the temperature of initial weightlessness is 307 ℃, and weightless 5% temperature is 403 ℃.
Embodiment 8
PEK-L, 0.22g (2mmol) Hydroxyethyl acrylate, 0.42g (2mmol) DCC, 0.02g (0.2mmol) DMAP and the 10mLTHF of 3.68g (7mmol) embodiment 1 preparation placed the there-necked flask of 100mL, and esterification is carried out in logical nitrogen and stirring under 25 ℃ temperature; Obtain flaxen suspension liquid behind the 24h; It is filtered the back under vigorous stirring, slowly pour in the mixing solutions that is made into by ethanol and hydrochloric acid and precipitate,, will precipitate the gained material and boil repeatedly and wash to remove residual DCC and DCU; Place vacuum drying oven dry again; Obtain white product, promptly have the polyaryletherketone of formula (I) structure, productive rate is 61%.
After obtaining white product, it is carried out nuclear magnetic resonance spectroscopy and IR spectroscopy, analytical results shows, the polyaryletherketone of gained white product for having formula (I) structure.
Measure gained according to method mentioned above and have the limiting viscosity of the polyaryletherketone of formula (I) structure, the result shows that its limiting viscosity is 0.29dL/g;
Measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure according to method mentioned above respectively; The result shows respectively; Its second-order transition temperature is 153 ℃, and the temperature of initial weightlessness is 310 ℃, and weightless 5% temperature is 409 ℃.
Can know by above embodiment, contain the propenyl ester group in the molecular structure of the polyaryletherketone with formula (I) structure provided by the invention, have more cross-linking set and good resistance toheat, can be used as products such as high temperature resistant type ultraviolet-curing paint.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.