CN104910361B - Double degradation polymer of a kind of polylactic acid light/water and preparation method thereof - Google Patents
Double degradation polymer of a kind of polylactic acid light/water and preparation method thereof Download PDFInfo
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- CN104910361B CN104910361B CN201510336322.8A CN201510336322A CN104910361B CN 104910361 B CN104910361 B CN 104910361B CN 201510336322 A CN201510336322 A CN 201510336322A CN 104910361 B CN104910361 B CN 104910361B
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Abstract
The invention belongs to new material technology field, the double degradation polymer of a kind of polylactic acid light/water, its structural formula is as follows:Its preparation method is, (1), by 2,6 dimethyl alcohol nitrobenzene matters and mercaptopropionic acid are dissolved in toluene, under catalyst, and condensing reflux, obtain 2,6 two (3 mercapto-propionate) nitrobenzene matters；(2) by the polylactic acid and 2 of two ends carbon-carbon double bonds, 6 two (3 mercapto-propionate) nitrobenzene matters is dissolved in chloroform, first reacts under conditions of ice bath, then temperature reaction, product is dried, i.e. obtains the double degradation polymer of light/water.Introducing o-nitrophenetole group to polylactic acid main chain, the polylactic acid of light/water double down solution character of being got everything ready by thiol-ene click chemistry legal system, preparation method is simple.Prepared polylactic acid can hydrolyze, and light degradation also can occur, and can be controlled the degradation speed of polylactic acid by illumination so that degradation rate is controlled.
Description
Technical field
The invention belongs to new material technology field, be specifically related to a kind of light/water-bis-degradation polymers
Method.
Background technology
Polylactic acid, is called for short PLA, also referred to as polylactide, belongs to polyester family, be with lactic acid
The high molecular polymer obtained it is polymerized for primary raw material.Polylactic acid raw material source abundance, Ke Yizai
Raw, and production process is pollution-free, and product can be with biodegradation, it is achieved following in nature
Ring, is therefore ideal Green Polymer Material.Polylactic acid has been applied to preparation group
The material of weaver's engineering support.But when requiring that support has different degradeds due to different tissue reconstructions
Between.But have very if only regulating the degradation rate of polylactic acid by molecular weight and molecualr weight distribution
Big limitation.Therefore, solving is that to realize polylactic acid wide to polylactic acid degradation speed control problem
One important prerequisite of general application.This is accomplished by being modified polylactic acid, makes polylactic acid possess
Some other new performance, widens its application.
Summary of the invention
The technical problem to be solved in the present invention is: overcome in prior art polylactic acid degradation rate not
Controlled deficiency, it is provided that double degradation polymer of a kind of polylactic acid light/water and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is: a kind of polylactic acid light/water
Double degradation polymers, its structural formula is as follows:
Wherein R1=R2=H, CH3、C2H5、C3H7, R3=H, CH3、C2H5、C3H7；U=1,2,3 ...；
n≥2。
The preparation method of the double degradation polymer of above-mentioned polylactic acid light/water, step is as follows:
(1) preparation of 2,6-bis-(3-mercapto-propionate) nitrobenzene matters；
By 2,6-dimethyl alcohol nitrobenzene matters and mercaptopropionic acid are dissolved in toluene, are urging
At agent catalysis, reaction temperature 120 DEG C, condensing reflux 12h, filters, revolves steaming, crude product
With dichloromethane dissolve, saturated sodium bicarbonate solution wash 3 times, anhydrous magnesium sulfate be dried, mistake
Filter, rotation are steamed, and obtain 2,6-bis-(3-mercapto-propionate) Nitrobenzol；
(2) preparation of the double degradation polymer of light/water
By polylactic acid and 2,6-bis-(3-mercapto-propionate) nitre of two ends carbon-carbon double key
Base benzene class material is dissolved in chloroform, first reacts 8～10h under conditions of ice bath, then rises
Product, to 30 DEG C of reaction 8h, is dried, i.e. obtains light/water-bis-degradation polymers by temperature.
Further, described 2/6-dimethyl alcohol nitrobenzene matters general structure is as follows:
Wherein R1=R2=H, CH3, C2H5, C3H7, R3=H, CH3, C2H5, C3H7。
As preferably, the catalyst described in step (1) is benzenesulfonic acid, p-methyl benzenesulfonic acid, fluorination
In boron or aluminum chloride any one.
As preferably, the polylactic acid molecule amount of the two ends carbon-carbon double key described in step (2) exists
In the range of 1000～20000.
As preferably, described 2,6-dimethyl alcohol nitrobenzene matters and mercaptopropionic acid mole
Ratio is 1:3～4, described 2,6-dimethyl alcohol nitrobenzene matters and described toluene molar volume
Ratio is 1:30～60mol/mL.
Further, the polylactic acid and 2 of described two ends carbon-carbon double key, 6-bis-(3-sulfydryl
Methyl propionate) nitrobenzene matters mol ratio is 1:1.
The invention has the beneficial effects as follows, introducing to polylactic acid main chain of the present invention has photodegradation
The o-nitrophenetole group of matter, has been got everything ready light/water-bis-by mercaptan-alkene clicking chemistry legal system
The polylactic acid of degraded character, preparation method is simple.Prepared polylactic acid can hydrolyze,
Light degradation also can occur, the degradation speed of polylactic acid can be controlled by illumination so that degraded speed
Rate is controlled.
Accompanying drawing explanation
The present invention is further described with embodiment below in conjunction with the accompanying drawings.
Fig. 1 is the nuclear-magnetism hydrogen of 2,6-bis-(3-mercapto-propionate) Nitrobenzol in embodiment 1
Spectrogram；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of double down hydrolysis products in embodiment 1；
Fig. 3 is the uv absorption figure of degradable material difference light application time in embodiment 1；
Fig. 4 is degradable material degradation curve under the conditions of illumination and not illumination in embodiment 1.
Detailed description of the invention
Embodiment 1
(1) preparation of 2,6-bis-(3-mercapto-propionate) Nitrobenzol
Weigh 2,6-dimethyl alcohol Nitrobenzol and the sulfydryl third of 3 molar fractions of 1 molar fraction
Acid is dissolved in the toluene of 30mL, 1%wt (compared to raw material) benzenesulfonic acid be catalyzed,
At reaction temperature 120 DEG C, condensing reflux 12h, filters, revolves steaming, crude product dichloromethane
Dissolve, saturated sodium bicarbonate solution wash 3 times, anhydrous magnesium sulfate be dried, filter, revolve steaming,
Obtaining 2,6-bis-(3-mercapto-propionate) Nitrobenzol, its nucleus magnetic hydrogen spectrum figure is as shown in Figure 1.
(2) preparation of light/water-bis-degradation polymers
Weigh 1 molar fraction, 1,000 molecular weight polylactic acid and 1 of two ends carbon-carbon double key rub
You are dissolved in the chloroform of 20mL by 2,6-bis-(3-mercapto-propionate) Nitrobenzol of mark
In, under conditions of ice bath, first react 8h, then be warming up to 30 DEG C of reaction 8h, by product
Being dried, i.e. obtain light/water-bis-degradation polymers, its general figure of nuclear-magnetism hydrogen is as shown in Figure 2.
As it is shown on figure 3, for above-mentioned preparation degradable material ultraviolet light irradiate 0s, 30s,
The uv absorption spectra of gained after 1min, 2min, 5min, 10min, 15min, from figure
In it can be seen that there is the ultraviolet absorption peak of nitro near 290nm, and along with irradiate time
Between increase, its uv absorption peak intensity is gradually increased, and wavelength gradually to wavelength increase side
To movement, illustrating that the photoresponse group on strand there occurs degraded, thing of i.e. changing products is to have light
The characteristic of response.
As shown in Figure 4, taking the degradable material of two groups of above-mentioned preparations, one group of every day is with light intensity
50mW/cm2Placing into culture medium hydrolysis after carrying out the irradiation of 15min, another group the most directly connects
Put into culture medium to be hydrolyzed.First day, the 3rd day, the 6th day, the tenth day, the 13rd
My god, the 16th day, Ahau, the 25th day and the 30th day take out, be dried and claim
Weight.
It can be seen that the hydrolysis rate of sample is crossed in illumination is significantly faster than that the sample of non-illumination.
Illustrate that this material has obvious double down solution character.
Embodiment 2
(1) preparation of 2,6-bis-(3-mercapto-propionate) Nitrobenzol
Weigh 2,6-dimethyl alcohol Nitrobenzol and the sulfydryl of 3 molar fractions of 1 molar fraction
Propanoic acid is dissolved in the toluene of 35mL, at the p-methyl benzenesulfonic acid of 1%wt (compared to raw material)
At catalysis, reaction temperature 120 DEG C, condensing reflux 12h, filter, revolve steaming, crude product is with two
Chloromethanes dissolves, saturated sodium bicarbonate solution wash 3 times, anhydrous magnesium sulfate be dried, filter,
Rotation is steamed, and obtains 2,6-bis-(3-mercapto-propionate) Nitrobenzol.
(2) preparation of light/water-bis-degradation polymers
Weigh 1 molar fraction, 3,000 molecular weight polylactic acid and 1 of two ends carbon-carbon double key
2,6-bis-(3-mercapto-propionate) Nitrobenzol of molar fraction is dissolved in the trichlorine of 25mL
In methane, under conditions of ice bath, first react 8.5h, then be warming up to 30 DEG C of reaction 8h, will be anti-
Answer product to be dried, i.e. obtain light/water-bis-degradation polymers.
Embodiment 3
(1) preparation of 2,6-bis-(3-mercapto-propionate)-4-methyl Nitrobenzol
Weigh the 2,6-dimethyl alcohol-4-methyl Nitrobenzol of 1 molar fraction and 3.5 moles points
The mercaptopropionic acid of number is dissolved in the toluene of 40mL, right at 1%wt (compared to raw material)
At toluenesulfonic acid catalysis, reaction temperature 120 DEG C, condensing reflux 12h, filters, revolves steaming, slightly
Product with dichloromethane dissolve, saturated sodium bicarbonate solution wash 3 times, anhydrous magnesium sulfate be dried,
Filter, rotation is steamed, and obtains 2,6-bis-(3-mercapto-propionate)-4-methyl Nitrobenzol.
(2) preparation of light/water-bis-degradation polymers
Weigh 1 molar fraction, 6,000 molecular weight polylactic acid and 1 of two ends carbon-carbon double key
2,6-bis-(3-the mercapto-propionate)-4-methyl Nitrobenzol of molar fraction is dissolved in 30mL's
In chloroform, under conditions of ice bath, first react 9h, then be warming up to 30 DEG C of reaction 8h, will
Product is dried, and i.e. obtains light/water-bis-degradation polymers.
Embodiment 4
(1) preparation of 2,6-bis-(3-mercapto-propionate)-4-methyl Nitrobenzol
Weigh the 2,6-dimethyl alcohol-4-methyl Nitrobenzol of 1 molar fraction and 3.5 moles points
The mercaptopropionic acid of number is dissolved in the toluene of 45mL, at the fluorine of 1%wt (compared to raw material)
Change at boron catalysis, reaction temperature 120 DEG C, condensing reflux 12h, filters, revolves steaming, crude product
With dichloromethane dissolve, saturated sodium bicarbonate solution wash 3 times, anhydrous magnesium sulfate be dried, mistake
Filter, rotation are steamed, and obtain 2,6-bis-(3-mercapto-propionate)-4-methyl Nitrobenzol.
(2) preparation of light/water-bis-degradation polymers
Weigh 1 molar fraction, 8,000 molecular weight polylactic acid and 1 of two ends carbon-carbon double key
2,6-bis-(3-the mercapto-propionate)-4-methyl Nitrobenzol of molar fraction is dissolved in 35mL
Chloroform in, under conditions of ice bath, first react 9.5h, then be warming up to 30 DEG C of reaction 8h,
Product is dried, i.e. obtains light/water-bis-degradation polymers.
Embodiment 5
(1) preparation of 2,6-bis-(3-mercapto-propionate)-3,5-dimethyl nitrobenzene
Weigh the 2,6-dimethyl alcohol-3,5-dimethyl nitrobenzene of 1 molar fraction and 4 moles
The mercaptopropionic acid of mark is dissolved in the toluene of 50mL, 1%wt's (compared to raw material)
At aluminum chloride-catalyzed, reaction temperature 120 DEG C, condensing reflux 12h, filters, revolves steaming, slightly produce
Thing with dichloromethane dissolve, saturated sodium bicarbonate solution wash 3 times, anhydrous magnesium sulfate be dried,
Filter, rotation is steamed, and obtains 2,6-bis-(3-mercapto-propionate)-3,5-dimethyl nitrobenzene.
(2) preparation of light/water-bis-degradation polymers
Weigh 1 molar fraction, 10,000 molecular weight polylactic acid and 1 of two ends carbon-carbon double key
2,6-bis-(3-the mercapto-propionate)-3,5-dimethyl nitrobenzene of molar fraction is dissolved in
In the chloroform of 40mL, under conditions of ice bath, first react 10h, then be warming up to 30 DEG C instead
Answer 8h, product is dried, i.e. obtain light/water-bis-degradation polymers.
Embodiment 6
(1) preparation of 2,6-bis-(3-mercapto-propionate)-3,5-dimethyl nitrobenzene
Weigh the 2,6-dimethyl alcohol-3,5-dimethyl nitrobenzene of 1 molar fraction and 4 moles
The mercaptopropionic acid of mark is dissolved in the toluene of 60mL, 1%wt's (compared to raw material)
At benzenesulfonic acid catalysis, reaction temperature 120 DEG C, condensing reflux 12h, filters, revolves steaming, slightly produce
Thing with dichloromethane dissolve, saturated sodium bicarbonate solution wash 3 times, anhydrous magnesium sulfate be dried,
Filter, rotation is steamed, and obtains 2,6-bis-(3-mercapto-propionate)-3,5-dimethyl nitrobenzene.
(2) preparation of light/water-bis-degradation polymers
Weigh 1 molar fraction, 20,000 molecular weight polylactic acid of two ends carbon-carbon double key and 1 mole
2,6-bis-(3-the mercapto-propionate)-3,5-dimethyl nitrobenzene of mark is dissolved in 50mL
Chloroform in, under conditions of ice bath, first react 10h, then be warming up to 30 DEG C of reaction 8h,
Product is dried, i.e. obtains light/water-bis-degradation polymers.
Claims (7)
1. the double degradation polymer of polylactic acid light/water, it is characterised in that: its structural formula is as follows:
Wherein R1=R2=H, CH3、C2H5、C3H7, R3=H, CH3、C2H5、C3H7；U=1,2,3 ...；
n≥2。
The preparation method of the double degradation polymer of polylactic acid light/water the most according to claim 1,
It is characterized in that: step is as follows:
(1) preparation of 2,6-bis-(3-mercapto-propionate) nitrobenzene matters；
By 2,6-dimethyl alcohol nitrobenzene matters and mercaptopropionic acid are dissolved in toluene, are urging
At agent catalysis, reaction temperature 120 DEG C, condensing reflux 12h, filter, revolve steaming, crude product is used
Dichloromethane dissolves, saturated sodium bicarbonate solution wash 3 times, anhydrous magnesium sulfate be dried, filter,
Rotation is steamed, and obtains 2,6-bis-(3-mercapto-propionate) Nitrobenzol；
(2) preparation of the double degradation polymer of light/water
By polylactic acid and 2,6-bis-(3-mercapto-propionate) nitro of two ends carbon-carbon double key
Benzene class material is dissolved in chloroform, first reacts 8～10h under conditions of ice bath, then heats up
To 30 DEG C of reaction 8h, product is dried, i.e. obtains light/water-bis-degradation polymers.
The preparation method of the double degradation polymer of polylactic acid light/water the most according to claim 2,
It is characterized in that: described 2,6-dimethyl alcohol nitrobenzene matters general structure is as follows:
Wherein R1=R2=H, CH3, C2H5, C3H7, R3=H, CH3, C2H5, C3H7。
The preparation method of the double degradation polymer of polylactic acid light/water the most according to claim 2,
It is characterized in that: the catalyst described in step (1) is benzenesulfonic acid, p-methyl benzenesulfonic acid, boron fluoride
Or in aluminum chloride any one.
The preparation method of the double degradation polymer of polylactic acid light/water the most according to claim 2,
It is characterized in that: the polylactic acid molecule amount of the two ends carbon-carbon double key described in step (2) exists
In the range of 1000～20000.
The preparation method of the double degradation polymer of polylactic acid light/water the most according to claim 2,
It is characterized in that: described 2,6-dimethyl alcohol nitrobenzene matters with mercaptopropionic acid mol ratio is
1:3～4, described 2,6-dimethyl alcohol nitrobenzene matters with described toluene molar volume ratio is
1:30～60mol/mL.
The preparation method of the double degradation polymer of polylactic acid light/water the most according to claim 2,
It is characterized in that: the polylactic acid of described two ends carbon-carbon double key and 2,6-bis-(3-mercaptopropionic acid
Methyl ester) nitrobenzene matters mol ratio is 1:1.
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Effective date of registration: 20201125 Address after: No. 159, Chengjiang Middle Road, Jiangyin City, Wuxi City, Jiangsu Province Patentee after: Jiangyin Intellectual Property Operation Co., Ltd Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |