Summary of the invention
The object of the present invention is to provide a kind of terminal hydroxy group polyacrylic ester linear or branching with the preparation of ATRP method is the polyacrylate-urethane copolymer of feedstock production and the method for preparation thereof.
The present invention with the molecular weight of ATRP method preparation be 500~10000 and molecular weight distribution narrower (molecular weight of polyacrylic ester can design as required, the specific design method is seen embodiment, one end of linear or branching molecular weight distribution<2.0) is the polyacrylic ester of hydroxyl for the Br the other end, with N-methyl monoethanolamine the end group bromine of polyacrylic ester is carried out nucleophilic substitution again, obtain the terminal hydroxy group polyacrylic ester.Then with terminal hydroxy group polyacrylic ester R ' (HO) n be raw material, exist under a certain amount of solvent or the condition of no solvent, with isocyanates R
1(OCN) n in certain temperature, adds under a certain amount of catalyzer or the catalyst-free condition and reacts, and has prepared to have molecular weight contains acrylate and ammonia ester structure more than 8000 and in the molecular backbone chain novel polyacrylate-urethane copolymer.
The synthetic route of polyacrylate-urethane copolymer is as follows:
Isocyanates R wherein
1(NCO) n is: diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), naphthalene-1,5-vulcabond, hexamethylene diisocyanate or 2,6-vulcabond methyl caproate (LDI), hexamethylene diisocyanate (HDI) etc.
Wherein R ' is a polyacrylic ester, shown in following graphic I of its structure (polyacrylic ester) or the formula II (polymethacrylate), as: the homopolymer or the multipolymer of the linear or branching of ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, methyl acrylate, methyl methacrylate, Dimethylaminoethyl Methacrylate etc.
Formula I formula II
Wherein R is an alkyl, and its carbon atom number is 1~8; The molecular weight of polyacrylic ester is 500~10000, and polymerization degree n corresponds to 3~200.
A kind of polyacrylate-urethane copolymer, its structural formula is
N=3~200 wherein, its molecular weight is more than 8000; R wherein
1Be alkyl or aryl, its carbon atom number is less than 25; R ' is a polyacrylic ester, and its molecular weight is 500~10000.
A kind of preparation method of acrylate-urethane copolymer, carry out according to following step:
A) preparation of terminal hydroxy group acrylate:
(1) acrylic ester monomer, organic halogen initiator, catalyzer, part and solvent are added in the reaction vessel, charge into nitrogen or argon gas after reaction system is vacuumized,, reacted under the magnetic agitation 6~15 hours at 50 ℃~120 ℃;
Wherein (1) described initiator is the halogenated organic compound, as alpha-brominated isopropylformic acid hydroxyl ethyl ester, alpha-brominated isopropylformic acid hydroxy butyl ester, alpha-brominated ethyl isobutyrate, tetramethylolmethane four alpha-brominated isobutyrates etc.; Wherein if with alpha-brominated isopropylformic acid hydroxyl ethyl ester, the organic halogen that end group such as alpha-brominated isopropylformic acid hydroxy butyl ester is Br be initiator then synthetic be linear polyacrylic ester, if with a plurality of end groups such as tetramethylolmethane four alpha-brominated isobutyrates be the organic halogen of Br be initiator then synthetic be the terminal hydroxy group polyacrylic ester of branching; Carry out the reaction of step (3) again, promptly can obtain the terminal hydroxy group polyacrylic ester of linear or branching respectively; Catalyzer is the low price metal halide catalyst, as CuBr, FeCl
2, FeBr
3Deng; Part is five methyl diethylentriamine (PMDETA); Wherein said solvent is ethyl acetate, toluene, tetrahydrofuran (THF) etc.
(1) described acrylic ester monomer wherein: initiator=2~100: 1 (mol ratio), low price metal halide catalyst: acrylic ester monomer=1~2: 100 (mol ratios), low price metal halide catalyst: part=1: 2 (mol ratio), 20%~35% of solvent load=system quality.
(2) product that obtains removes and desolvates and catalyzer, obtains the polyacrylate(s) oligopolymer.
(3) above-mentioned polyacrylate(s) oligopolymer, properties-correcting agent, triethylamine are added in the reaction vessel, charge into nitrogen or argon gas after reaction system is vacuumized,, reacted under the magnetic agitation 8~48 hours at 50 ℃~120 ℃; Wherein (3) described properties-correcting agent is N-methyl monoethanolamine; N-methyl monoethanolamine wherein: polymkeric substance=25~100: 1 (mol ratio), triethylamine: polymkeric substance=5~20: 1 (mol ratio).
(4) products therefrom carries out pickling, washing, and extraction, to remove excessive N-methyl monoethanolamine, drying obtains (HO) n of terminal hydroxy group polyacrylic ester R ', and its molecular weight is 500-10000, molecular weight distribution<2.0;
B) preparation of polyacrylate-urethane copolymer
(5) add above-mentioned terminal hydroxy group polyacrylic ester R ' (HO) n, the solvent of preparing in reaction vessel, heating and stirring make polymkeric substance be dissolved in the solvent fully;
(6) treat that system temperature rises to 60 ℃~70 ℃, add the isocyanic ester R of certain mass
1(OCN) n, and add catalyzer or do not add catalyzer, continuing to be warming up to 80 ℃~110 ℃, and keep this thermotonus 3~8h, question response can obtain flaxen polyacrylate-urethane copolymer after finishing; Wherein said R ' is n and R (HO)
1(OCN) n is according to-NCO/-OH=1: 1 (mol ratio) feeds intake; Wherein (6) described catalyzer is: the mixture of one or more in dibutyl tin laurate, stannous octoate, the triethylene diamine; Wherein said isocyanates material can be vulcabond or polyisocyanates, as: 4,4 '-diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), naphthalene-1,5-vulcabond (NDI), hexamethylene diisocyanate (HDI), 2,6-vulcabond methyl caproate (LDI) etc.Wherein said solvent is: organic solvents such as vinyl acetic monomer, butanone, toluene, its consumption are (HO) 0~10 times of n quality of R '.
The present invention has following advantage and beneficial effect:
1. the terminal hydroxy group polyacrylic ester utilizes the preparation of ATRP method, can guarantee that the molecular weight of polymeric polymkeric substance is controlled distinct with structure.
2. the present invention proposes utilizes the method for terminal hydroxy group polyacrylic ester for the feedstock production polyacrylate-urethane copolymer, at first according to different needs design preparation different molecular weight, different types of terminal hydroxy group polyacrylic ester, molecular weight does not wait from 500~10000, as the terminal hydroxy group polyethyl acrylate, the terminal hydroxy group butyl polyacrylate, different monooctyl ester of terminal hydroxy group polyacrylic acid and terminal hydroxy group block acrylic polymer etc., terminal hydroxy group polyacrylic ester with preparation is raw material and isocyanates reaction again, thereby has obtained containing in the main chain the novel polyacrylate-urethane copolymer of acrylate and ammonia ester structure.
3. the present invention proposes utilize the terminal hydroxy group polyacrylic ester for the molecular weight of the polyacrylate-urethane copolymer of feedstock production more than 8000, polymkeric substance has solvability preferably, mechanical property, adhesive property and thermal stability etc. have the advantage separately of acrylate and urethane.
Embodiment
The method of design of terminal hydroxy group polyacrylic ester raw molecule amount:
Mn
Polymkeric substance=M
Monomer* (m
Monomer/ M
Monomer)/(m
Initiator/ M
Initiator* initiator purity/N
Br)+M
Initiator
Wherein:
Mn
Polymkeric substance: the molecular weight of terminal hydroxy group polyacrylic ester raw material
M
Monomer: the acrylate monomer molecular weight
M
Initiator: the molecular weight of organic halogen initiator
m
Monomer: the acrylate monomer quality
m
Initiator: the quality of organic halogen initiator
N
Br: the quantity that contains the Br that can cause the ATRP reaction in the initiator
Fig. 1,2,3 is 2000 for designing molecular weight, GPC (gel permeation chromatograph) test result of class linear-shaped terminal hydroxyl polyacrylic ester not of the same race, by test result as can be seen, the terminal hydroxy group polyacrylic ester molecular weight size of preparation conforms to substantially with the molecular weight of design, and molecular weight distribution is narrower.
By to the preparation polyacrylate-urethane copolymer the GPC test result as can be seen, utilize the lower terminal hydroxy group polyacrylic ester of molecular weight, can synthesize polyacrylate-urethane copolymer with higher molecular weight.
Can test out the polyacrylate-urethane copolymer second-order transition temperature of preparation by DSC (differential scanning calorimeter) test result of polyacrylate-urethane copolymer to preparation.
By to the preparation polyacrylate-urethane copolymer TGA (thermogravimetric analyzer) test result as can be seen, the thermal decomposition process of the polyacrylate-urethane copolymer of preparation mainly contains two stages, first thermolysis stage is ammonia ester bond segmental thermolysis in the main chain, second thermolysis stage is the thermolysis of the different monooctyl ester segmental of polyacrylic acid, and it is higher that the polyacrylate-urethane copolymer of preparation gets initial decomposition temperature, better heat stability.
Following example is to further specify of the present invention.
Embodiment 1:(is feedstock production polyethyl acrylate-urethane copolymer with the linear-shaped terminal hydroxyl polyethyl acrylate of molecular weight 2000)
(1) preparation of molecular weight 2000 linear polyethyl acrylates
Polymerization formula: initiator (alpha-brominated isopropylformic acid hydroxy butyl ester): monomer (ethyl propenoate): catalyzer: part=1: 23.3: 0.233: 0.465 (mol ratio), adding equals the toluene of monomer mass 20% as solvent again.
Polymerization procedure: in the 100ml four-hole boiling flask of thermometer, magnetic stir bar is housed, add ethyl propenoate monomer 20g (0.2326mol), the alpha-brominated isopropylformic acid hydroxy butyl ester of initiator 2.65g (0.01mol, purity 93%), solvent toluene 4g, Catalysts Cu Br0.335g (0.00233mol), part PMDETA0.80g (0.00465mol) mixes, system is vacuumized logical nitrogen, react 10h down at 65 ℃~70 ℃.After reaction finishes, with the vinyl acetic monomer diluted polymer, remove the catalyzer in the polymkeric substance, remove solvent in the system through underpressure distillation then, obtain faint yellow transparent little thickness product, quality product is 20.27g, and productive rate is 90.2%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=2185 of polyethyl acrylate, molecular weight distribution PDI=1.16.
(2) preparation of molecular weight 2000 linear-shaped terminal hydroxyl polyethyl acrylates
Polymerization formula: polyethyl acrylate: N-methyl monoethanolamine: triethylamine=1: 25: 5 (mol ratio).
Polymerization procedure: polymkeric substance 15.68g (0.00784mol), N-methyl monoethanolamine 14.70g (0.196mol), the triethylamine 3.96g (0.039mol) of preparation in the step (1) are added in the 100ml four-hole boiling flask; system is mixed; vacuumize logical nitrogen, react 24h down for about 90 ℃ in nitrogen protection.After reaction finishes, through extraction, anhydrous MgSO
4Drying, filtration, parlkaline Al
2O
3Processes such as post are removed excessive N-methyl monoethanolamine, remove solvent in the system through underpressure distillation again, obtain faint yellow transparent little thickness product at last.Product quality is 9.5g, productive rate 61.1%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=2493 of terminal hydroxy group polyethyl acrylate, molecular weight distribution PDI=1.32.
(3) preparation of polyethyl acrylate-urethane copolymer
Polymerization formula: terminal hydroxy group polyethyl acrylate: tolylene diisocyanate (TDI)=1: 1 (mol ratio), the butanone that adds 2 times of quality of terminal hydroxy group polyethyl acrylate again is as solvent.
Polymerization procedure: with the terminal hydroxy group polyethyl acrylate 9.56g (0.0038mol) of preparation in the step (2), butanone 10g puts into the 100ml four-hole boiling flask, heated and stirred is dissolved it fully, about 50 ℃, add 0.653g (0.0038mol) TDI, and adding catalyzer triethylene diamine, keep about 80 ℃ reactions 3 hours, reaction can obtain faint yellow heavy-gravity polymkeric substance after finishing, solvent in the faint yellow thick polymkeric substance of preparation is removed, obtained having the polyethyl acrylate-urethane copolymer of certain degree of hardness at last.It is carried out the GPC test, and the polyethyl acrylate that obtains preparing-urethane copolymer number-average molecular weight is 10106; The DSC test, (gpc analysis of the terminal hydroxy group polyethyl acrylate raw material of molecular weight 2000 is seen accompanying drawing 1 for-0.83 ℃ to obtain second-order transition temperature, the gpc analysis of ethyl propenoate-urethane copolymer is seen accompanying drawing 4, TGA analyzes and sees accompanying drawing 7, dsc analysis is seen accompanying drawing 10, and infrared absorption spectra is seen accompanying drawing 15).
Embodiment 2:(is feedstock production butyl polyacrylate-urethane copolymer with the linear-shaped terminal hydroxyl butyl polyacrylate of molecular weight 2000)
(1) preparation of molecular weight 2000 linear polypropylene acid butyl esters
Polymerization formula: initiator (alpha-brominated isopropylformic acid hydroxy butyl ester): monomer (butyl acrylate): catalyzer: part=1: 14.4: 0.125: 0.251 (mol ratio), adding equals the toluene of monomer mass 20% as solvent again.
Polymerization procedure: in the 100ml four-hole boiling flask of thermometer, magnetic stir bar is housed, add Butyl Acrylate Monomer 103.95g (0.812mol), the alpha-brominated isopropylformic acid hydroxy butyl ester of initiator 13.5g (0.0565mol, purity 90%), solvent toluene 20g, Catalysts Cu Br1.02g (0.00708mol), part PMDETA
2.45g (0.0142mol), mix, system is vacuumized logical nitrogen, react 9h down at 60 ℃~65 ℃.After reaction finishes, with the vinyl acetic monomer diluted polymer, remove the catalyzer in the polymkeric substance, remove solvent in the system through underpressure distillation then, obtain faint yellow transparent little thickness product, quality product is 105g, and productive rate is 90.4%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=2225 of butyl polyacrylate, molecular weight distribution PDI=1.18.
(2) preparation of molecular weight 2000 linear-shaped terminal hydroxyl butyl polyacrylates
Polymerization formula: butyl polyacrylate: N-methyl monoethanolamine: triethylamine=1: 25: 5 (mol ratio).
Polymerization procedure: polymkeric substance 105g (0.0525mol), N-methyl monoethanolamine 98.5g (1.31mol), the triethylamine 26.5g (0.262mol) of preparation in the step (1) are added in the 500ml four-hole boiling flask; system is mixed; vacuumize logical nitrogen, react 24h down for about 90 ℃ in nitrogen protection.After reaction finishes, through extraction, anhydrous MgSO
4Drying, filtration, parlkaline Al
2O
3Processes such as post are removed excessive N-methyl monoethanolamine, remove solvent in the system through underpressure distillation again, obtain faint yellow transparent little thickness product at last.Product quality is 53g, productive rate 50.5%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=1990 of terminal hydroxy group butyl polyacrylate, molecular weight distribution PDI=1.24.
(3) preparation of butyl polyacrylate-urethane copolymer
Polymerization formula: terminal hydroxy group butyl polyacrylate: tolylene diisocyanate (TDI)=1: 1 (mol ratio), the toluene that adds 2 times of terminal hydroxy group butyl polyacrylate quality again is as solvent.
Polymerization procedure: with the terminal hydroxy group butyl polyacrylate 5.373g (0.0027mol) of preparation in the step (2), toluene 9g puts into the 100ml four-hole boiling flask, heated and stirred is dissolved it fully, about 70 ℃, add 0.451g (0.026mol) TDI, keep about 80 ℃ reactions about 3.5 hours, reaction can obtain faint yellow thick polymkeric substance after finishing, and the solvent in the faint yellow heavy-gravity polymkeric substance of preparation is removed, and obtains having the butyl polyacrylate-urethane copolymer of certain degree of hardness at last.It is carried out the GPC test, and the butyl polyacrylate that obtains preparing-urethane copolymer number-average molecular weight is 9729; The DSC test, (gpc analysis of the terminal hydroxy group butyl polyacrylate raw material of molecular weight 2000 is seen accompanying drawing 2 for-8.03 ℃ to obtain second-order transition temperature, the gpc analysis of butyl acrylate-urethane copolymer is seen accompanying drawing 5, TGA analyzes and sees accompanying drawing 8, dsc analysis is seen accompanying drawing 11, and infrared absorption spectra is seen accompanying drawing 16).
Embodiment 3:(is the different monooctyl ester-urethane copolymer of feedstock production polyacrylic acid with the different monooctyl ester of linear-shaped terminal hydroxyl polyacrylic acid of molecular weight 2000)
(1) preparation of the different monooctyl ester of molecular weight 2000 linear polyacrylic acid
Polymerization formula: initiator (alpha-brominated isopropylformic acid hydroxy butyl ester): monomer (Isooctyl acrylate monomer): catalyzer: part=1: 10: 0.126: 0.253 (mol ratio), adding equals the toluene of monomer mass 20% as solvent again.
Polymerization procedure: in the 500ml four-hole boiling flask of thermometer, magnetic stir bar is housed, add Isooctyl acrylate monomer monomer 162.13g (0.88mol), the alpha-brominated isopropylformic acid hydroxy butyl ester of initiator 21g (0.0879mol, purity 90%), solvent toluene 32.35g, Catalysts Cu Br 1.60g (0.0111mol), part PMDETA3.85g (0.0222mol) mixes, system is vacuumized logical nitrogen, react 8h down at 60 ℃~65 ℃.After reaction finishes, with the vinyl acetic monomer diluted polymer, remove the catalyzer in the polymkeric substance, remove solvent in the system through underpressure distillation then, obtain faint yellow transparent little thickness product, quality product is 170g, and productive rate is 93.9%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=2410 of the different monooctyl ester of polyacrylic acid, molecular weight distribution PDI=1.22.
(2) preparation of the different monooctyl ester of molecular weight 2000 linear-shaped terminal hydroxyl polyacrylic acid
Polymerization formula: the different monooctyl ester of polyacrylic acid: N-methyl monoethanolamine: triethylamine=1: 25: 5 (mol ratio).
Polymerization procedure: polymkeric substance 170g (it is 0.085mol that molecular weight calculates its mole number according to design load 2000), N-methyl monoethanolamine 159g (2.12mol), the triethylamine 42.9g (0.42mol) of preparation in the step (1) are added in the 500ml four-hole boiling flask; system is mixed; vacuumize logical nitrogen, react 24h down for about 90 ℃ in nitrogen protection.After reaction finishes, through extraction, anhydrous MgSO
4Drying, filtration, parlkaline Al
2O
3Processes such as post are removed excessive N-methyl monoethanolamine, remove solvent in the system through underpressure distillation again, obtain faint yellow transparent little thickness product at last.Product quality is 90g, productive rate 52.9%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=2347 of the different monooctyl ester of terminal hydroxy group polyacrylic acid, molecular weight distribution PDI=1.19.
(3) preparation of the different monooctyl ester-urethane copolymer of polyacrylic acid
Polymerization formula: the different monooctyl ester of terminal hydroxy group polyacrylic acid: tolylene diisocyanate (TDI)=1: 1 (mol ratio) because the different monooctyl ester viscosity of terminal hydroxy group polyacrylic acid is less, therefore needn't adds solvent and reduce reaction system viscosity.Polymerization procedure: the different monooctyl ester 2.976g of terminal hydroxy group polyacrylic acid (0.00127mol) of preparation in the step (2) is put into the 50ml there-necked flask, heating is also stirred, when rising to, temperature adds 0.216g (0.00124mol) TDI when 50 ℃ of left and right sides polymer viscosities hang down, and adding catalyzer dibutyl tin laurate, keep about 80 ℃ reactions about 3 hours, reaction 2 hours about elevated temperature to 95 ℃ again, reaction can obtain faint yellow heavy-gravity polymkeric substance after finishing, and this faint yellow thick polymkeric substance is the different monooctyl ester-urethane copolymer of the polyacrylic acid that will prepare.It is carried out the GPC test, the different monooctyl ester of the polyacrylic acid that obtains preparing-urethane copolymer number-average molecular weight is that 10223 (gpc analysis of the different monooctyl ester raw material of terminal hydroxy group polyacrylic acid of molecular weight 2000 is seen accompanying drawing 3, hydrogen spectrum nmr spectrum is seen accompanying drawing 13, the gpc analysis of Isooctyl acrylate monomer-urethane copolymer is seen accompanying drawing 6, TGA analyzes and sees accompanying drawing 9, dsc analysis is seen accompanying drawing 12, and hydrogen spectrum nmr spectrum is seen accompanying drawing 14, and infrared absorption spectra is seen accompanying drawing 17).
Embodiment 4:(is feedstock production butyl polyacrylate-urethane copolymer with the linear-shaped terminal hydroxyl butyl polyacrylate of molecular weight 10000)
(1) preparation of molecular weight 10000 linear butyl polyacrylates
Polymerization formula: initiator (alpha-brominated isopropylformic acid hydroxy butyl ester): monomer (butyl acrylate): catalyzer: part=1: 79: 1.185: 2.37 (mol ratios), adding equals the vinyl acetic monomer of system quality 30% as solvent again.
Polymerization procedure: in the 500ml four-hole boiling flask of thermometer, magnetic stir bar is housed, add the alpha-brominated ethyl isobutyrate of 0.96g (0.004mol) initiator, 48.79g monomer butyl acrylate (0.381mol), 0.68g (0.0047mol) Catalysts Cu Br, 1.64g (0.0095mol) part PMDETA, 20.84g solvent vinyl acetic monomer, mix, system is vacuumized logical nitrogen, stirring reaction is 13 hours under 90 ℃ oil bath.Reaction finishes, and with the vinyl acetic monomer diluted polymer, removes the catalyzer in the polymkeric substance, removes solvent in the system through underpressure distillation then, obtains faint yellow transparent little thickness product, quality product 45g, productive rate 90.5%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=12643 of butyl polyacrylate, molecular weight distribution PDI=1.54.
(2) preparation of molecular weight 10000 linear-shaped terminal hydroxyl butyl polyacrylates
Polymerization formula: butyl polyacrylate: N-methyl monoethanolamine: triethylamine=1: 25: 5 (mol ratio).
Polymerization procedure: polymkeric substance 21.8g (0.0017mol), 9.7g (0.13mol) N-methyl monoethanolamine, 2.3g (0.023mol) triethylamine of preparation in the step (1) are added in the reaction vessel; mix; vacuumize logical nitrogen, reacted 8 hours down for about 90 ℃ in nitrogen protection.After reaction finishes, through extraction, anhydrous MgSO
4Drying, filtration, parlkaline Al
2O
3Processes such as post are removed excessive N-methyl monoethanolamine, remove solvent in the system through underpressure distillation again, obtain faint yellow transparent little thickness product at last.Quality product is 6.9g, and productive rate is 31.7%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=13533 of terminal hydroxy group butyl polyacrylate, molecular weight distribution PDI=1.48.
(3) preparation of butyl polyacrylate-urethane copolymer
Polymerization formula: terminal hydroxy group butyl polyacrylate: isophorone diisocyanate (IPDI)=1: 1 (mol ratio), the toluene that adds 3 times of terminal hydroxy group butyl polyacrylate quality again is as solvent.
Polymerization procedure: the terminal hydroxy group butyl polyacrylate 6.5g (0.00065mol) of preparation in the step (2) is put into the 50ml there-necked flask, heating is also stirred, when rising to 50 ℃ of left and right sides, temperature adds 0.145g (0.000653mol) IPDI, and the inferior tin of adding octoate catalyst, keep about 100 ℃ reactions about 3 hours, reaction can obtain faint yellow heavy-gravity polymkeric substance after finishing, and this faint yellow thick polymkeric substance is the butyl polyacrylate-urethane copolymer that will prepare.
Embodiment 5:(is feedstock production polymethylmethacrylablock block butyl acrylate-urethane copolymer with the linear-shaped terminal hydroxymethyl methyl acrylate block butyl acrylate of molecular weight 3000)
When (1) preparation of molecular weight 3000 linear methyl methacrylate block butyl acrylate copolymer prepares methyl methacrylate block butyl acrylate copolymer, adopt and feed in raw material for twice.
Polymerization formula: initiator (alpha-brominated isopropylformic acid hydroxy butyl ester): monomer 1 (methyl methacrylate): catalyzer 1: ligand 1: monomer 2 (butyl acrylate): catalyzer 2: part 2=1: 7.5: 0.075: 0.15: 17.6: 0.176: 0.352 (mol ratio), and the reaction initial adding equal the toluene of initial system quality 20% as solvent.
Polymerization procedure: in the 150ml four-hole boiling flask, add the alpha-brominated isopropylformic acid of 5.0g (0.021mol) initiator (4-hydroxyl butyl ester), 15.9g monomers methyl methacrylate (0.159mol), 0.21g (0.0015mol) Catalysts Cu Br, 0.5g (0.0029mol) part PMDETA, 3.0g solvent toluene mixes.System vacuum nitrogen filling gas, stirring reaction is 24 hours under 50 ℃ oil bath.In flask, add 45.4g (0.35mol) butyl acrylate after 24 hours, 0.51g (0.0035mol) CuBr, 1.22g (0.007mol) part PMDETA, after taking out true inflated with nitrogen once more, continued stirring reaction 24 hours under 80 ℃ of oil baths, reaction finishes, after removing catalyzer and solvent, can obtain faint yellow transparent little thickness product, quality product 56g, productive rate 85%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=4302 of butyl polyacrylate, molecular weight distribution PDI=1.35.
(2) preparation of molecular weight 3000 linear-shaped terminal hydroxymethyl methyl acrylate block butyl acrylate copolymer
Polymerization formula: methyl methacrylate and butyl acrylate segmented copolymer: N-methyl monoethanolamine: triethylamine=1: 25: 5 (mol ratio).
Polymerization procedure: in reaction vessel, add methyl methacrylate and butyl acrylate segmented copolymer in 20.22g (0.0047mol) step (1), 12.71g (0.169mol) N-methyl monoethanolamine, 3.37g (0.037mol) triethylamine mixes.System vacuum nitrogen filling gas reacted 24 hours down for about 90 ℃ in nitrogen protection.Reaction finishes the back pickling, and extraction oil reservoir in washing back is crossed post after utilizing anhydrous MgSO4 drying, removes solvent at last, obtains the faint yellow thickness transparent products of 6.5g.Productive rate 32%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=2716 of terminal hydroxy group methyl methacrylate block butyl acrylate copolymer, molecular weight distribution PDI=1.84.
(3) preparation of polymethylmethacrylablock block butyl acrylate-urethane copolymer
Polymerization formula: terminal hydroxy group butyl polyacrylate: diphenylmethanediisocyanate (MDI)=1: 1 (mol ratio), the toluene that adds 2 times of terminal hydroxy group butyl polyacrylate quality again is as solvent.
Polymerization procedure: the terminal hydroxy group methyl methacrylate block butyl acrylate copolymer 3.1g (0.00114mol) of preparation in the step (2) is put into the 50ml there-necked flask, heating is also stirred, when rising to 50 ℃ of left and right sides, temperature adds 0.287g (0.001145mol) MDI, and adding catalyzer triethylenediamine, keep about 100 ℃ reactions about 3 hours, reaction can obtain faint yellow heavy-gravity polymkeric substance after finishing, and this faint yellow thick polymkeric substance is the polymethylmethacrylablock block butyl acrylate-urethane copolymer that will prepare.
Embodiment 6:(is feedstock production butyl polyacrylate-urethane copolymer with molecular weight 500 linear-shaped terminal hydroxyl butyl polyacrylates)
(1) preparation of molecular weight 500 linear butyl polyacrylates
Polymerization formula: initiator (alpha-brominated isopropylformic acid hydroxy butyl ester): monomer (butyl acrylate): catalyzer: part=1: 2.4: 0.048: 0.096 (mol ratio), adding equals the vinyl acetic monomer of system quality 25% as solvent again.
Polymerization procedure: in the 500ml four-hole boiling flask of thermometer, magnetic stir bar is housed, add the alpha-brominated isopropylformic acid hydroxy butyl ester of 128.94g (0.66mol) initiator, 202.37g monomer butyl acrylate (1.58mol), 4.59g (0.032mol) Catalysts Cu Br, 11.05g (0.064mol) part PMDETA, 86.74g solvent vinyl acetic monomer, mix, system is vacuumized logical nitrogen, stirring reaction is 8 hours under 70 ℃ oil bath.Reaction finishes, and with the vinyl acetic monomer diluted polymer, removes the catalyzer in the polymkeric substance, removes solvent in the system through underpressure distillation then, obtains faint yellow transparent little thickness product, quality product 304.4g, productive rate 91.9%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=583 of butyl polyacrylate, molecular weight distribution PDI=1.09.
(2) preparation of molecular weight 500 linear-shaped terminal hydroxyl butyl polyacrylates
Polymerization formula: butyl polyacrylate: N-methyl monoethanolamine: triethylamine=1: 25: 5 (mol ratio).
Polymerization procedure: polymkeric substance 19.63g (0.034mol), 69.4g (0.925mol) N-methyl monoethanolamine, 19.2g (0.190mol) triethylamine of preparation in the step (1) are added in the reaction vessel; mix; vacuumize logical nitrogen, reacted 8 hours down for about 90 ℃ in nitrogen protection.After reaction finishes, through extraction, anhydrous MgSO
4Drying, filtration, parlkaline Al
2O
3Processes such as post are removed excessive N-methyl monoethanolamine, remove solvent in the system through underpressure distillation again, obtain faint yellow transparent little thickness product at last.Quality product is 6.7g, and productive rate is 34%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=642 of terminal hydroxy group butyl polyacrylate, molecular weight distribution PDI=1.09.
(3) preparation of butyl polyacrylate-urethane copolymer
Polymerization formula: terminal hydroxy group butyl polyacrylate: diphenylmethanediisocyanate (MDI)=1: 1 (mol ratio).
Polymerization procedure: with the molecular weight of preparation is 642, molecular weight distribution is that 1.09 terminal hydroxy group butyl polyacrylate 6.5g (0.0101mol) puts into the 50ml there-necked flask, heating is also stirred, when rising to 50 ℃ of left and right sides, temperature adds 2.6g (0.0104mol) MDI, and adding catalyzer dibutyl tin laurate, keep about 90 ℃ reactions about 3 hours, reaction can obtain faint yellow heavy-gravity polymkeric substance after finishing, and this faint yellow thick polymkeric substance is the butyl polyacrylate-urethane copolymer that will prepare.
Embodiment 7:(is feedstock production butyl polyacrylate-urethane copolymer with molecular weight 6,000 three branched hydroxyl butyl polyacrylates)
(1) preparation of molecular weight 6,000 three end butyl polyacrylates
Polymerization formula: initiator (trimethylolpropane tris (alpha-brominated isobutyrate)): monomer (butyl acrylate): catalyzer: part=1: 45: 0.45: 0.9 (mol ratio), adding equals the vinyl acetic monomer of system quality 30% as solvent again.
Polymerization procedure: in the 150ml four-hole boiling flask, add 3.49g (0.006mol) initiator trimethylolpropane tris (alpha-brominated isobutyrate), 34.85g monomer butyl acrylate (0.27mol), 0.39g (0.0027mol) Catalysts Cu Br, 0.93g (0.0054mol) part PMDETA, 12.4g the solvent vinyl acetic monomer mixes.System vacuum nitrogen filling gas, stirring reaction is 8 hours under 70 ℃ oil bath.Reaction finishes, remove catalyzer and solvent after, can obtain faint yellow transparent little thickness product, quality product 32.6g, productive rate 85%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=5487 of butyl polyacrylate, molecular weight distribution PDI=1.18.
(2) preparation of molecular weight 6,000 three terminal hydroxy group butyl polyacrylates
Modified formula: butyl polyacrylate: N-methyl monoethanolamine: triethylamine=1: 75: 15 (mol ratio).
Modification procedure: in the 150ml four-hole boiling flask, add butyl polyacrylate in 14.45g (0.0026mol) example 13,15.7g (0.21mol) N-methyl monoethanolamine, 4.3g (0.043mol) triethylamine mixes.System vacuum nitrogen filling gas, stirring reaction is 8 hours under 70 ℃ the oil bath.Reaction finishes the back pickling, and extraction oil reservoir in washing back utilizes anhydrous MgSO
4Post is crossed in dry back, removes solvent at last, obtains the faint yellow thickness transparent products of 8.7g.Productive rate 60%.Product is carried out the GPC test, obtain the number-average molecular weight Mn=5813 of terminal hydroxy group butyl polyacrylate, molecular weight distribution PDI=1.3.
(3) preparation of butyl polyacrylate-urethane copolymer
Polymerization formula: terminal hydroxy group butyl polyacrylate: tolylene diisocyanate (TDI)=1: 1 (mol ratio).
Polymerization procedure: with the molecular weight of preparation is 5813, molecular weight distribution is that 1.3 three terminal hydroxy group butyl polyacrylate 8.5g (0.00146mol) put into the 100ml there-necked flask, heating is also stirred, when rising to 50 ℃ of left and right sides, temperature adds 0.256g (0.00147mol) TDI, and adding catalyzer dibutyl tin laurate, keep about 90 ℃ reactions about 3 hours, reaction can obtain faint yellow heavy-gravity polymkeric substance after finishing, and this faint yellow thick polymkeric substance is the butyl polyacrylate-urethane copolymer that will prepare.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Those skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for the modification that the present invention makes according to announcement of the present invention.