Can cause styrene oligomer diphenyl ketone type light trigger of radio polymerization and preparation method thereof
Technical field
The present invention relates to cause radio polymerization initiator field, particularly relate to styrene oligomer diphenyl ketone type light trigger that can cause radio polymerization and preparation method thereof.
Background technology
Radiation (or light) initiator is the important component of radiation curing system, and present industrialized photocuring system, light trigger are the solidification rate of decision system and the important factor of state of cure.But traditional light trigger is the small molecules that contains optical active group, relatively poor with the polymer phase capacitive, moreover, remain in light trigger and photolysis debris migration and volatilization easily in the product, make the product aging yellowing, smell and toxicity occur, restricted the application of photocuring system at aspects such as food and drug packages.The light trigger that relative molecular weight is bigger is the effective way that addresses the above problem, and causes that countries in the world extensively note, develops research one after another, is the important topic of current light trigger research field.Common macromolecular photoinitiator type mainly contains positively charged ion salt and benzophenone class, phenylacetic aldehyde esters of gallic acid, acylphosphanes oxygen class, benzil class, Alpha-hydroxy ketone, alpha-amino group ketone etc.
In above-mentioned macromolecular photoinitiator, the styrene oligomer macromolecular photoinitiator is noticeable.Meticulous and specialty chemicals, phase p18 had reported styrene oligomer type macromolecular photoinitiator in 2000 the 19th, and a kind of is the light trigger that styrene dimer or trimerization form the phenyl indan class, and its general formula is:
Wherein:
N=0,1; R, R
1, R
2=C
1~C
3Alkyl; R
3, R
4=C
1~C
8Alkyl; X=Cl, OH, OR.
Second kind is that vinylbenzene carries out the oligomeric styrene type graftomer that obtains, and its general formula is:
The polymerization degree of this polymkeric substance is common also lower, and the polymerization degree of business-like Lamberti KIP150 is 4.Although above-mentioned these two kinds of light triggers have solved the weak point of existing small molecules light trigger to a certain extent, but these two kinds of light triggers also do not reach the satisfactory performance index, still can not substitute existing product fully, they are of limited application simultaneously, and shortcoming on the high side has also further limited their promotion and application.
Summary of the invention
The objective of the invention is to overcome the deficiency that above-mentioned prior art exists, be engaged in the development research of light trigger for many years through the contriver, the investigation of the production practice and the market requirement, exploitation provide a kind of active high, efficiency of initiation is high, volatility is low, anti-transport property and consistency is good, odorlessness and toxic styrene oligomer diphenyl ketone type light trigger that causes radio polymerization and preparation method thereof.
The styrene oligomer diphenyl ketone type light trigger that causes radio polymerization provided by the invention is characterized in that its chemical structural formula is:
Wherein X be can with the monomer of vinylbenzene or substituted phenylethylene copolymerization, olefines for example is as ethene, propylene, divinyl, isoprene; Esters of acrylic acid is as methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid-α-hydroxyl ethyl ester, senecioate-hydroxyl ethyl ester, vinylformic acid hydroxy butyl ester; Methyl acrylic ester is as methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid-α-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid hydroxy butyl ester; Anhydrides is as MALEIC ANHYDRIDE; Vinyl cyanide; Be preferably divinyl, isoprene, (methyl) methyl acrylate, (methyl) butyl acrylate or vinyl cyanide.
This comonomer X can be identical or different; N is 2 to 20 integer, according to the reaction conditions difference, forms different number n (or claiming the polymerization degree) vinylbenzene or the homopolymerization of substituted phenylethylene or the mixture of copolymerized oligomer; The R substituting group is hydrogen, methyl, ethyl, chloromethyl, brooethyl, methylol, hydroxyl, halogen such as fluorine, chlorine, bromine, and nitro, phenyl or benzyl are preferably hydrogen, methyl, chloromethyl, hydroxyl, chlorine or bromine;
R
1, R
2Or R
3Substituting group is respectively the substituting group of hydrogen, methyl, ethyl, chloromethyl, brooethyl, methylol, hydroxyl, alkoxyl group such as methoxyl group, oxyethyl group, tert.-butoxy, octyloxy, halogen such as fluorine, chlorine, bromine, nitro, phenyl, benzyl, sulfur-bearing such as methylthio group, ethylmercapto group, rosickyite base, thiophenyl, to methylbenzene sulfenyl, carboxyl, methoxycarbonyl or sulfonic group; R
1, R
2Or R
3Can be identical or different, be preferably hydrogen, methyl, ethyl, chloromethyl, chlorine, bromine, methylthio group, thiophenyl or to the methylbenzene sulfenyl;
On the phenyl ring of oligomer molecules chain; proportioning according to oligopolymer and acylating agent is different; grafting 1-n benzoyl part (two arone class formation parts); thereby form the mixture of macromolecular photoinitiator molecular weight 400-5000; so have the consistency of resin better; and its absorption band is wideer, and application prospect is widely arranged.
The preparation method who causes the styrene oligomer diphenyl ketone type light trigger of radio polymerization provided by the invention generally includes the following step:
(1) preparation of oligopolymer
In the container that organic solvent such as ethylene dichloride, oil of mirbane equal solvent are housed; in the presence of superoxide such as benzoyl peroxide or Diisopropyl azodicarboxylate; add vinylbenzene or substituted phenylethylene continuously; temperature of reaction 50-90 ℃; reaction times 3-6 hour; suitably the molar ratio of control superoxide such as benzoyl peroxide or Diisopropyl azodicarboxylate and vinylbenzene or substituted phenylethylene is 0.02: 1 to 0.1: 2; and adding speed; can obtain different molecular weight or polymerization degree n; for example molecular weight is 400-5000, the oligopolymer of n=2-20.Perhaps pass through vinylbenzene or substituted phenylethylene in the presence of organolithium, in solvent as benzene, hexanaphthene, raffinate oil, paraffins mixture etc., carry out living anion polymerization and prepare the homopolymer or the multipolymer of oligopolymer, wherein the cinnamic molar ratio of lithium alkylide and vinylbenzene or replacement is 0.025: 1 to 0.25: 1, described organolithium is lithium alkylide such as lithium ethide, propyl lithium, n-Butyl Lithium, isobutyl-lithium, two lithiums of phenyl lithium, naphthalene lithium or two lithium such as divinyl or the two lithiums of isoprene etc.
(2) preparation of styrene oligomer diphenyl ketone type light trigger
In having the reaction vessel of stirring; usually in dithiocarbonic anhydride or oil of mirbane equal solvent; the vinylbenzene or substituted phenylethylene (straight chain) oligopolymer that add step (1); in the presence of aluminum trichloride (anhydrous); with acylating agent such as Benzoyl chloride or substituted benzoyl chloride; to methyl benzoyl chloride; parachlorobenzoyl chloride; parabromobenzoyl chloride; 2; 4; reactions such as 6-tri-methyl chloride and 4-(4 '-aminomethyl phenyl) thiobenzoyl chlorine; temperature of reaction 30-80 ℃; reaction times 2-6 hour, the molar ratio of control acylating agent and oligopolymer was 0.05: 1 to 1: 1, adding speed and add-on; obtain the mix products of different grafting acylating agent groups; carry out layering then, successively with NaOH or KOH and water washing, dry vinylbenzene or the substituted phenylethylene oligomer diphenyl ketone type light trigger of getting.
In the styrene oligomer diphenyl ketone type light trigger and method for making thereof that causes radio polymerization provided by the invention; with vinylbenzene or substituted phenylethylene homopolymerization or with linearity (straight chain) oligopolymer of copolymerization monomer copolymerization gained be parent; on the phenyl ring of linear oligomer chain, introduce the group that benzoyl or substituted benzoyl (two arone classes) have radiation initiation function; (macromole) light trigger of gained is a polymerization degree difference; two arone class formations; the percentage of grafting difference; molecular weight has the mixture of the macromolecular photoinitiator of radiation initiating activity from 400-5000; solve existing small molecules two arone light triggers migration and volatilization easily; smell and toxic technical barrier occur, make macromolecular photoinitiator provided by the invention have both the excellent specific property of former peculiar light-initiated performance of small molecules two arone classes and macromolecular photoinitiator.Described oligopolymer comprises molecular weight from 400 to 5000, low molecular weight phenylethylene or substituted phenylethylene homopolymerization or the copolymerized oligomer of polymerization degree n=2 to 20, the homopolymer of preference such as vinylbenzene, alpha-methyl styrene, ethyl styrene, bromstyrol or chloro-styrene, or with random copolymers, segmented copolymer or alternating copolymer etc. of divinyl, isoprene, (methyl) methyl acrylate etc.Described benzoyl part (two arone structure divisions) comprise with vinylbenzene or substituted phenylethylene oligomer chain phenyl ring on grafting form and have the benzoyl part of two arone structure divisions; in preparation process; by adopting different acylating agents (two arone structures) the benzoyl part that obtains having different structure; be preferably benzoyl, to methyl benzoyl, to chlorobenzene formacyl, to benzoyl bromide, 2; 4,6-trimethylbenzoyl and 4-(4 '-aminomethyl phenyl) thiobenzoyl etc.Corresponding acylating agent is Benzoyl chloride, to methyl benzoyl chloride, parachlorobenzoyl chloride, parabromobenzoyl chloride, 2,4,6-tri-methyl chloride and 4-(4 '-aminomethyl phenyl) thiobenzoyl chlorine etc.Different according to vinylbenzene or substituted phenylethylene oligopolymer and acylating agent proportioning, can grafting one or more until n benzoyl part, thus form the macromolecular photoinitiator of molecular weight 400 to 5000.According to the different application field, select different benzoyls partly to obtain various styrene oligomer diphenyl ketone type light triggers with caused radio polymerization of benzophenone structural functional group.
The characteristics that cause the styrene oligomer diphenyl ketone type light trigger of radio polymerization provided by the invention are:
1, this light trigger structure is small molecules diphenyl ketone type light trigger to be caused the group of radio polymerization function and macromole styrene oligomer in structure to combine and have the macromolecular photoinitiator of unique texture, makes this initiator have both the excellent properties that the distinctive activity of small molecules benzophenone and macromole are had.
2, light trigger of the present invention is synthetic easy, and cost is low.
3, light trigger of the present invention is based on the initiator of oligopolymer, therefore has than higher molecular weight, so volatility is smaller, does not have smell.
4, light trigger of the present invention can well solve conventional initiator problem of residual concentration in the product after curing, and therefore anti-transport property is good, and toxicity is little, and environment compatibility is better.
5, light trigger of the present invention says with resin system that from structure certain similarity is arranged, and therefore compares with traditional small molecules light trigger, and it and resin system have better consistency, and absorption band is wideer, use more extensive.
6, light trigger of the present invention itself is colourless, when being applied to the radio polymerization of olefinic type monomers, the flavescence phenomenon can not take place.
Light trigger of the present invention can be widely used on food and the pharmaceutical packing printing-ink or in other plastic working.
Accompanying drawing is described
Fig. 1 is the infrared spectrogram of benzoyl polystyrene linear oligomer
Fig. 2 is the infrared spectrogram to poly-(vinylbenzene-methyl methacrylate) linear oligomer of methyl benzoyl
Fig. 3 is the infrared spectrogram to chlorobenzene formacyl polyvinyltoluene linear oligomer
Fig. 4 is the infrared spectrogram of 4 '-aminomethyl phenyl-4-thiobenzoyl base polystyrene linear oligomer
Fig. 5 is for being the efficiency of initiation figure of light trigger with benzoyl polystyrene linear oligomer
Embodiment
The present invention further specifies the present invention with the following example, but protection scope of the present invention is not limited to embodiment.Can make many other variation and modifications in the case of without departing from the spirit and scope of protection of the present invention to those skilled in the art, still be included in the scope of protecting in claims.
The preparation of embodiment 1, benzoyl polystyrene linear oligomer
To being furnished with agitator, having the separating funnel of calcium chloride tube and be connected with in the 2L there-necked flask of the reflux exchanger that absorbs gas device, add the 720ml ethylene dichloride, stir and add 40g benzoyl peroxide and 200ml vinylbenzene down again, be warming up to about 4 hours of 80 ℃ of reactions, obtain the polystyrene oligomer solution.Be cooled to room temperature, add the 265g aluminum trichloride (anhydrous) in batches and be warming up to 40 ℃ under stirring.Under high degree of agitation, drip 238g (200ml) Benzoyl chloride.After reaction begins to emit hydrogenchloride, stop heating, continue to add Benzoyl chloride, time spent 4h.Refluxed then one hour, be cooled to room temperature after, under agitation, slowly go into just to the 5kg trash ice, tell the upper strata oil reservoir, use 5% sodium hydroxide solution and water washing successively, anhydrous magnesium sulfate drying.After reclaiming solvent, use the small amount of ethanol cleaning product, obtain target product 293g after the drying, yield 82%, its infrared spectrogram is as shown in Figure 1.
Embodiment 2,2,4, the preparation of 6-trimethylbenzoyl polystyrene linear oligomer
To being furnished with agitator, having the separating funnel of calcium chloride tube and be connected with in the 2L there-necked flask of the reflux exchanger that absorbs gas device, add the 720ml ethylene dichloride, stir and add 40g benzoyl peroxide and 200ml vinylbenzene down again, be warming up to about 4 hours of 80 ℃ of reactions, obtain the polystyrene oligomer solution.Be cooled to room temperature, add the 265g aluminum trichloride (anhydrous) in batches and be warming up to 40 ℃ under stirring.Under high degree of agitation, drip 300g 2,4, the 6-tri-methyl chloride.After reaction begins to emit hydrogenchloride, stop heating, continue to add 2,4,6-tri-methyl chloride, time spent 5.5h.Refluxed then one hour, be cooled to room temperature after, under agitation, slowly go into just to the 5kg trash ice, tell the upper strata oil reservoir, use 5% sodium hydroxide solution and water washing successively, anhydrous magnesium sulfate drying.After reclaiming solvent, use the small amount of ethanol cleaning product, obtain target product 325g after the drying, yield 77%.
Example 3, to the preparation of poly-(vinylbenzene-methyl methacrylate) linear oligomer of methyl benzoyl
To being furnished with agitator, having the separating funnel of calcium chloride tube and be connected with in the 1L there-necked flask of the reflux exchanger that absorbs gas device, add 350ml dithiocarbonic anhydride, stir and add 25g benzoyl peroxide and 150ml vinylbenzene and 50ml methyl methacrylate down again, be warming up to about 4 hours of 60 ℃ of reactions, gathered (vinylbenzene-methyl methacrylate) solution.Be cooled to room temperature, add the 140g aluminum trichloride (anhydrous) in batches and be warming up to 35 ℃ under stirring.Under high degree of agitation, drip 110g (93ml) to methyl benzoyl chloride.After reaction begins to emit hydrogenchloride, stop heating, continue to add to methyl benzoyl chloride time spent 3h.Refluxed then one hour, be cooled to room temperature after, under agitation, slowly go into just to the 3kg trash ice, tell the upper strata oil reservoir, use 5% sodium hydroxide solution and water washing successively, anhydrous magnesium sulfate drying.After reclaiming solvent, use the small amount of ethanol cleaning product, obtain target product 148g after the drying, yield 56%, its infrared spectrogram is as shown in Figure 2.
The preparation of embodiment 4, poly-(styrene-propene acid butyl ester) linear oligomer of benzoyl
To being furnished with agitator, having the separating funnel of calcium chloride tube and be connected with in the 1L there-necked flask of the reflux exchanger that absorbs gas device, add 350ml dithiocarbonic anhydride, stir and add 28g benzoyl peroxide and 150ml vinylbenzene and 70ml butyl acrylate down again, be warming up to about 3.5 hours of 55 ℃ of reactions, gathered (styrene-propene acid butyl ester) solution.Be cooled to room temperature, add the 140g aluminum trichloride (anhydrous) in batches and be warming up to 35 ℃ under stirring.Under high degree of agitation, drip 100g (83ml) Benzoyl chloride.After reaction begins to emit hydrogenchloride, stop heating, continue to add Benzoyl chloride, time spent 4h.Refluxed then one hour, be cooled to room temperature after, under agitation, slowly go into just to the 3kg trash ice, tell the upper strata oil reservoir, use 5% sodium hydroxide solution and water washing successively, anhydrous magnesium sulfate drying.After reclaiming solvent, use the small amount of ethanol cleaning product, obtain target product 130g after the drying, yield 48%.
Embodiment 5, to the preparation of chlorobenzene formacyl polyvinyltoluene linear oligomer
Get 1 of exsiccant polymerizing pipe, mix single hole soft rubber ball and short Glass tubing and one section rubber tubing, connect in the anhydrous and oxygen-free operating system, vacuumize, applying argon gas, three times repeatedly, to get rid of air in the test tube.Connect argon system then, with ice bath polymerizing pipe is cooled to 5 ℃, inject 4mL anhydrous cyclohexane 1.8mL and dry vinyl toluene and 1.2mL n-Butyl Lithium (2.8M) solution by syringe respectively from rubber tubing, shake up, solution becomes orange, after stirring 30min, add the small amount of methanol termination reaction.Color disappears immediately.Reaction solution is dropped in the methyl alcohol of 30mL, the adularescent precipitation generates immediately, filters, and uses the methanol wash after drying, gets white solid 1.5g, yield 93%.
To being furnished with agitator, having the separating funnel of calcium chloride tube and be connected with in the 1L there-necked flask of the reflux exchanger that absorbs gas device, add 500ml dithiocarbonic anhydride, under agitation add the above-mentioned polyvinyltoluene linear oligomer of 50g, after the system for the treatment of mixes, add the 66g aluminum trichloride (anhydrous) in batches and be warming up to 35 ℃.Under high degree of agitation, drip 70g (51ml) parachlorobenzoyl chloride.After reaction begins to emit hydrogenchloride, stop heating, continue to add parachlorobenzoyl chloride, time spent 4h.Refluxed then one hour, be cooled to room temperature after, under agitation, slowly go into just to the 3kg trash ice, tell the upper strata oil reservoir, use 5% sodium hydroxide solution and water washing successively, anhydrous magnesium sulfate drying.After reclaiming solvent, use the small amount of ethanol cleaning product, dry afterwards with obtaining target product 70g, yield 66%, its infrared spectrogram is as shown in Figure 3.
The preparation of embodiment 6,4-(4 '-aminomethyl phenyl) thiobenzoyl base polystyrene linear oligomer
To being furnished with agitator, having the separating funnel of calcium chloride tube and be connected with in the 1L there-necked flask of the reflux exchanger that absorbs gas device, add 250ml oil of mirbane, stir and add 30g benzoyl peroxide and 250ml vinylbenzene down again, be warming up to about 4 hours of 55 ℃ of reactions, obtain polystyrene solution.Be cooled to room temperature, add the 350g aluminum trichloride (anhydrous) in batches and be warming up to 50 ℃ under stirring.Under high degree of agitation, drip the solution of 400g 4-(4 '-aminomethyl phenyl) thiobenzoyl chlorine in 250ml oil of mirbane.Keep temperature of reaction at 50 ℃, dropwise in 5 hours, back flow reaction is 2 hours again.After being cooled to room temperature, under agitation, slowly go into just to the 5kg trash ice, tell the upper strata oil reservoir, use 5% sodium hydroxide solution and water washing successively, anhydrous magnesium sulfate drying.After reclaiming solvent, use the small amount of ethanol cleaning product, obtain target product 387g after the drying, yield 68%, its infrared spectrogram is as shown in Figure 4.
Embodiment 7, to the preparation of poly-(styrene butadiene) straight-chain block copolymer of bromoformyl
Get 1 of exsiccant polymerizing pipe, mix single hole soft rubber ball and short Glass tubing and one section rubber tubing, connect in the anhydrous and oxygen-free operating system, vacuumize, applying argon gas, three times repeatedly, to get rid of air in the test tube.Connect argon system then, with ice bath polymerizing pipe is cooled to 5 ℃, inject 4mL anhydrous cyclohexane 1.5mL dry benzene ethene and 1.0mL n-Butyl Lithium (2.8M) solution by syringe respectively from rubber tubing, shake up, solution becomes orange, behind the stirring 30min, with the speed feeding exsiccant divinyl 1.0g of 1mL/min, lead to the back and stirred 15min, added the small amount of methanol termination reaction.Color disappears immediately.Reaction solution is dropped in the methyl alcohol of 30mL, the adularescent precipitation generates immediately, filters, and uses the methanol wash after drying, gets white solid 2.2g, yield 94%.
To being furnished with agitator, having the separating funnel of calcium chloride tube and be connected with in 50 there-necked flasks of the reflux exchanger that absorbs gas device, add poly-(styrene butadiene) segmented copolymer of 20ml dithiocarbonic anhydride and 2.0g, add the 1.5g aluminum trichloride (anhydrous) again and be warming up to 40 ℃.Stir down, drip 1.9g (1.3mL) parabromobenzoyl chloride.Keep temperature of reaction at 40 ℃, dropwise in 0.5 hour, back flow reaction is 1.5 hours again.After being cooled to room temperature, under agitation, slowly go into just to the 0.5kg trash ice, tell the upper strata oil reservoir, use 5% sodium hydroxide solution and water washing successively, anhydrous magnesium sulfate drying.After reclaiming solvent, use the small amount of ethanol cleaning product, obtain target product 2.8g after the drying, yield 88%.
Embodiment 8, benzoyl polystyrene linear oligomer uv-light polymerization efficiency test
With benzoyl polystyrene linear oligomer light trigger with available from two vinylformic acid (TPGDA) monomers of the tripropylene glycol of U.S. Sartomer company and N, N-mesitylenic acid ethyl ester is by 0.2: 100: 0.2 mixed, stirs system is mixed.(Nicolet 5700 by the real-time infrared spectroscopy instrument that is equipped with KBr beam splitter and MTC/A detector for the sample kinetics of polymerization reaction, Thermo Electron, USA) detect in real time, the high-energy UV-light pointolite of 300~500nm wave band is by fiber orientation irradiation sample 15min, irradiation energy is 130mw/cm, (Honle UV technology Germany) records by light intensity meter.In the photopolymerization process, data gathering is spaced apart 0.3985s, and acquisition resolution is 4cm
-1, by OMNIC 7.5 software processes, the gained collection of illustrative plates as shown in Figure 5 at last.Can make 95% monomer finish polymerization in about as we can see from the figure 0.5 minute.