CN108530640A - Rosin propynyl ester internal plasticization PVC material and preparation method thereof - Google Patents
Rosin propynyl ester internal plasticization PVC material and preparation method thereof Download PDFInfo
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- CN108530640A CN108530640A CN201810399154.0A CN201810399154A CN108530640A CN 108530640 A CN108530640 A CN 108530640A CN 201810399154 A CN201810399154 A CN 201810399154A CN 108530640 A CN108530640 A CN 108530640A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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Abstract
Rosin propynyl ester internal plasticization PVC material and preparation method thereof, such rosin propynyl ester is synthesized to obtain by a series of rosin derivatives and propargyl bromide.Then from branches of the PVC of different Azides through click chemistry reactive grafting to PVC, by increasing the distance of PVC chains, reduce the interaction force of PVC main chains, increase the mobility between main chain, and then achieve the purpose that be plasticized PVC.The glass transition temperature of PVC product can be reduced to 32 DEG C by this method, and in distilled water, acid solution, aqueous slkali, vegetable oil esters and organic solvent without the migration of plasticizer.
Description
Technical field
The invention belongs to chemosynthesis technical fields, specifically about rosin propynyl ester reactive plasticizer and its internal plasticization PVC
The preparation method of material, more particularly to a kind of plasticizing PVC material with excellent solvent resistant extraction and volatility resistance energy.
Background technology
Polyvinyl chloride (PVC) is one of the thermoplastic polymer being most widely used in the world, by the end of 2012, the whole world
The consumption figure of polyvinyl chloride has reached 37,000,000 tons.It is excellent to assign product that a large amount of plasticizer will be added in usual PVC product
Mechanical property.The plasticising of adjacent benzene class esters is yield and the maximum plastic additive of consumption figure in the world, adjacent phenyl ester class plasticising in 2017
The dosage of agent accounts for the 70% of all plasticizer total amounts.Due to adjacent benzene class plasticizer during PVC product use be easy be precipitated or
It is extracted out by solvent, the property of product is made to change, seriously affected the service life of product, and human health brought latent
It is threatening.Recently, some scholars research is drawn a conclusion, and adjacent phenyl ester class plasticizer connects during PVC product use through human body
Touch, can the number of ways such as oral, respiratory tract, venous transfusion enter human body, to the toxic effect of the multiple systems of body, recognized
To be a kind of environment incretion interference factor.Therefore, the country such as US and European has limited adjacent benzene class plasticizer in medical treatment
The fields such as instrument, toy for children, packaging material for food use.In addition to this, since adjacent benzene class plasticizer is all from petrochemical industry
Resource, with the exhaustion of fossil resources, the pattern that plasticizer is synthesized using fossil resources is unsustainable.
The mode of plasticizing PVC product is predominantly blended at present, i.e. PVC and plasticizer directly by thermoplastic, solvent cast or
The modes physical mixed such as dry-mixing, this preparation method cannot prevent plasticiser from losing.The mode of another kind plasticizing PVC is internal
Monomer with plastication is exactly grafted on the branch of PVC by chemically reacting, passes through increase by plasticizing, i.e. internal plasticization
The distance of PVC interchains weakens the interaction force of interchain, increases the being mutually shifted property of interchain, and reduce PVC chains has normality, into
And PVC product is made macroscopically to show flexible and easy to process performance, achieve the purpose that be plasticized PVC product.This plasticizing
The benefit of mode is no migration of plasticizer, and the property of PVC product can be made to maintain a long-term stability, and is decreased since plasticizer is analysed
Go out brought to human body it is potentially hazardous.
Rosin is the glassy brittle substance that the secretion (rosin) of pine tree obtains after turpentine oil is distilled off, mainly at
It is resin acid to divide, and accounts for 90% of gross mass or more.About 25,000,000 km of China's pine forest area2, can adopt every year 2000000 tons of ester amount with
On, it is maximum rosin production state and exported country in the world.Rosin acid can carry out diels-Alder (Diels-
Alder) addition reaction, esterification, substitution reaction and acylation reaction etc. for example emulsify for synthesizing a variety of fine chemical products
Agent, thermosetting resin and liquid crystal material etc..Plasticizer is synthesized using rosin, China has raw material advantage.In recent years, has scholar
Plasticizer is synthesized through direct esterification reaction using rosin and long-chain alcohol, the vitrifying which can effectively reduce PVC product turns
Temperature.In consideration of it, reactive plasticizer is synthesized using rosin and its derivative, without the added value that can improve rosin, Er Qieke
It realizes and prepares the purpose without migration of plasticizer PVC material.
Invention content
The technical issues of solution：A kind of rosin propynyl ester internal plasticization PVC material of present invention offer and preparation method thereof, the material
Expect that there is excellent solvent resistant extraction and volatility resistance energy.
Technical solution：Rosin propynyl ester internal plasticization PVC material, chemical structural formula are as follows：
The preparation method of above-mentioned rosin propynyl ester internal plasticization PVC material, by rosin propynyl ester and Azide PVC through clickization
After learning reaction, then through methanol/distilled water solution washing of precipitate, obtained after drying；Reaction temperature is 10 DEG C -120 DEG C；Reaction time
For 0.15h-36h；In reaction process, the mass ratio of rosin propynyl ester and Azide PVC are (0.1-4):1, react required solvent
For nitrogen nitrogen dimethylformamide, tetrahydrofuran, acetone, dichloromethane or cyclohexanone；Catalyst needed for reaction is cuprous bromide, iodate
Cuprous and 1, at least one of 11 carbon -7- alkene of 8- diazabicylos, dosage is rosin propynyl ester and Azide PVC gross masses
1%-15%.
Above-mentioned rosin propynyl ester is synthesized by rosin or its derived product and 3- propargyl bromides.
Above-mentioned rosin derivative is abietic acid, neoabietic acid, the abietic acid that comes into leaves, levopimaric acid, dehydroabietic acid, pimaric acid, different sea
At least one of loose acid, sandaracopimaric acid.
Above-mentioned Azide PVC is made by PVC and sodium azide, and reaction temperature is 10 DEG C -80 DEG C, reaction time 0.1h-
12h, reaction dissolvent are nitrogen nitrogen dimethylformamide.The mass ratio of PVC and sodium azide is 1:(0.5-2).Used solvent
The ratio of quality and reactant gross mass is 1:(5-20).
Advantageous effect：The present invention synthesizes reactive plasticizer with forest products characteristic resources rosin, by it so that the mode of valence link is anti-
In the chemical constitution for the PVC chains answered, the internal plasticization PVC material with good solvent resistant extraction and resistance to volatilization is synthesized.Achievable pair
The higher value application of forest products characteristic resources rosin, obtained internal plasticization PVC material is to the higher PVC product of life requirement
Field has application value.Internal plasticization PVC material softness produced by the present invention and easy to process, can be reduced in process
Energy consumption.Also fewer for the research of internal plasticization PVC material both at home and abroad at present, the present invention can expand the use scope of PVC material,
It the development of internal plasticizing mechanism and improves there is directive function.
Description of the drawings
Fig. 1 is the infrared spectrogram of PVC；
Fig. 2 is the infrared spectrogram of Azide PVC；
Fig. 3 is differential scanning calorimeter (DSC) curve of PVC；
Fig. 4 is the DSC curve of internal plasticization PVC material prepared by embodiment 1.
Specific implementation mode
Embodiment 1
The synthesis of the vertical sour propynyl ester of dehydrogenation
The vertical acid of 0.1mol dehydrogenations and 0.113mol potassium carbonate are dissolved in 50mL acetone, 20 DEG C of stirrings, are instilled in 20min
The solution of 0.178mol propargyl bromides and 15mL acetone, after be warming up to 70 DEG C of back flow reactions 12 hours.Reaction solution is down to room temperature, makes
It is dissolved with dichloromethane, makes to be washed with distilled water 2 times, vacuum distillation obtains rosin propynyl ester.
The synthesis of Azide PVC
2g PVC and 2g sodium azide is dissolved in 150mL nitrogen nitrogen dimethylformamides, 60 DEG C be stirred to react 2 hours after be down to room
Temperature.Using methanol and distillation water washing, drying obtains Azide PVC.The infrared spectrum of PVC and Azide PVC respectively such as Fig. 1 and
Shown in Fig. 2.
The preparation of the vertical sour propynyl ester internal plasticization PVC material of dehydrogenation
2g Azides PVC, 0.22g cuprous bromide, 0.18g 1,11 carbon -7- alkene of 8- diazabicylos, the vertical acid of 4g dehydrogenations
Propynyl ester is dissolved in 80mL nitrogen nitrogen dimethylformamides, and nitrogen protection, 35 DEG C are stirred to react for 24 hours, filtration catalytic agent, using methanol and
Internal plasticization PVC material is obtained after distilled water washing and drying.Fig. 3 and Fig. 4 is respectively internal plasticization PVC materials prepared by PVC and this example
The DSC curve of material.Using the method for solvent cast, internal plasticization PVC material film is prepared by solvent of tetrahydrofuran.Using same
Method prepare dioctyl phthalate/PVC film (mass ratio 6:10).The articles Films of certain mass are immersed respectively
In n-hexane solvent, 50 DEG C maintain drying in two hours to weigh, and plasticizer mass loss percentage are calculated, to evaluate internal plasticization
The solvent resistant extraction performance of PVC material, the results are shown in Table 1.
Embodiment 2
It comes into leaves and indulges the synthesis of sour propynyl ester
0.1mol is come into leaves into vertical acid and 0.113mol potassium carbonate is dissolved in 50mL acetone, 20 DEG C of stirrings, is instilled in 20min
The solution of 0.178mol propargyl bromides and 15mL acetone, after be warming up to 70 DEG C of back flow reactions 12 hours.Reaction solution is down to room temperature, makes
It is dissolved with dichloromethane, makes to be washed with distilled water 2 times, vacuum distillation obtains rosin propynyl ester.
The synthesis of Azide PVC
2g PVC and 2g sodium azide is dissolved in 150mL nitrogen nitrogen dimethylformamides, and 60 DEG C are stirred to react 2 hours and are down to room
Temperature.Using methanol and distillation water washing, drying obtains Azide PVC.The infrared spectrum of PVC and Azide PVC respectively such as Fig. 1 and
Shown in Fig. 2.
The preparation for the vertical sour propynyl ester internal plasticization PVC material that comes into leaves
2g Azides PVC, 0.22g cuprous bromide, 0.18g 1,11 carbon -7- alkene of 8- diazabicylos, 4g come into leaves vertical sour
Propynyl ester is dissolved in 80mL nitrogen nitrogen dimethylformamides, and nitrogen protection, 35 DEG C are stirred to react for 24 hours, filtration catalytic agent, using methanol and
Internal plasticization PVC material is obtained after distilled water washing and drying.Using the method for solvent cast, interior increase is prepared by solvent of tetrahydrofuran
Mould PVC material film.Dioctyl phthalate/PVC film (mass ratio 6 is prepared using same method:10).Respectively will
The articles Films of certain mass immerse in n-hexane solvent, and 50 DEG C maintain drying in two hours to weigh, and calculate plasticizer mass loss
Percentage the results are shown in Table 1. to evaluate the solvent resistant extraction performance of internal plasticization PVC material
Embodiment 3
The synthesis of maleopimaric acid propynyl ester
0.1mol maleopimaric acids and 0.113mol potassium carbonate are dissolved in 50mL acetone, 20 DEG C of stirrings, are instilled in 20min
The solution of 0.178mol propargyl bromides and 15mL acetone, is warming up to 70 degree of back flow reactions 12 hours.Reaction solution is down to room temperature, uses
Dichloromethane dissolve, after make to be washed with distilled water 2 times, vacuum distillation obtain rosin propynyl ester.
The synthesis of Azide PVC
2g PVC and 2g sodium azide is dissolved in 150mL nitrogen nitrogen dimethylformamides, and 60 DEG C are stirred to react 2 hours and are down to room
Temperature.Using methanol and distillation water washing, drying obtains Azide PVC.The infrared spectrum of PVC and Azide PVC respectively such as Fig. 1 and
Shown in Fig. 2.
The preparation of maleopimaric acid propynyl ester internal plasticization PVC material
2g Azides PVC, 0.22g cuprous bromide, 0.18g 1,11 carbon -7- alkene of 8- diazabicylos, the Malaysias 4g Korean pine
Sour propynyl ester is dissolved in 80mL nitrogen nitrogen dimethylformamides, nitrogen protection, and 35 DEG C are stirred to react for 24 hours, and filtration catalytic agent uses methanol
With internal plasticization PVC material is obtained after distilled water washing and drying.Using the method for solvent cast, using tetrahydrofuran as in solvent preparation
Plasticized PVC materials film.Dioctyl phthalate/PVC film (mass ratio 6 is prepared using same method:10).Respectively
The articles Films of certain mass are immersed in n-hexane solvent, 50 DEG C maintain drying in two hours to weigh, and calculate plasticizer quality damage
It loses percentage and the results are shown in Table 1. to evaluate the solvent resistant extraction performance of internal plasticization PVC material
Embodiment 4
The synthesis of sandaracopimaric acid propynyl ester
0.1mol sandaracopimaric acids and 0.113mol potassium carbonate are dissolved in 50mL acetone, 20 DEG C of stirrings, are instilled in 20min
The solution of 0.178mol propargyl bromides and 15mL acetone, is warming up to 70 DEG C of back flow reactions 12 hours.Reaction solution is down to room temperature, uses
Dichloromethane dissolve, after make to be washed with distilled water 2 times, vacuum distillation obtain rosin propynyl ester.
The synthesis of Azide PVC
2g PVC and 2g sodium azide is dissolved in 150mL nitrogen nitrogen dimethylformamides, and 60 DEG C are stirred to react 2 hours and are down to room
Temperature.Using methanol and distillation water washing, drying obtains Azide PVC.The infrared spectrum of PVC and Azide PVC respectively such as Fig. 1 and
Shown in Fig. 2.
The preparation of sandaracopimaric acid propynyl ester internal plasticization PVC material
2g Azides PVC, 0.22g cuprous bromide, 0.18g 1,11 carbon -7- alkene of 8- diazabicylos, the mountains 4g reach Korean pine
Sour propynyl ester is dissolved in 80mL nitrogen nitrogen dimethylformamides, nitrogen protection, and 35 DEG C are stirred to react for 24 hours, and filtration catalytic agent uses methanol
With internal plasticization PVC material is obtained after distilled water washing and drying.DSC curve shows that the glass transition temperature of PVC is 85 DEG C, interior increasing
The glass transition temperature for moulding PVC material is 32 DEG C.Using the method for solvent cast, internal plasticization is prepared by solvent of tetrahydrofuran
PVC material film.Dioctyl phthalate/PVC film (mass ratio 6 is prepared using same method:10).Respectively by one
The articles Films for determining quality immerse in n-hexane solvent, and 50 DEG C maintain drying in two hours to weigh, and calculate plasticizer mass loss hundred
Ratio is divided to the results are shown in Table 1 to evaluate the solvent resistant extraction performance of internal plasticization PVC material.
The performance of internal plasticization PVC material prepared by 1 PVC of table and embodiment
The glass transition temperature of PVC product can be reduced to 32 DEG C by the present invention, and in distilled water, acid solution, alkali
In solution, vegetable oil esters and organic solvent without the migration of plasticizer.
Claims (7)
1. rosin propynyl ester internal plasticization PVC material, it is characterised in that chemical structural formula is as follows：
2. the preparation method of rosin propynyl ester internal plasticization PVC material described in claim 1, it is characterised in that by rosin propynyl ester and
Azide PVC is obtained after click chemistry reacts, then through methanol/distilled water solution washing of precipitate after drying；Reaction temperature is 10
℃-120℃；Reaction time is 0.15h-36h；In reaction process, the mass ratio of rosin propynyl ester and Azide PVC are (0.1-
4):1, it is nitrogen nitrogen dimethylformamide, tetrahydrofuran, acetone, dichloromethane or cyclohexanone to react required solvent；Catalysis needed for reaction
Agent is cuprous bromide, cuprous iodide and 1, and at least one of 11 carbon -7- alkene of 8- diazabicylos, dosage is rosin propynyl ester
With the 1%-15% of Azide PVC gross masses.
3. the preparation method of rosin propynyl ester internal plasticization PVC material according to claim 2, it is characterised in that the rosin third
Alkynes ester is synthesized by rosin or its derived product and 3- propargyl bromides.
4. the preparation method of rosin propynyl ester internal plasticization PVC material according to claim 3, it is characterised in that the rosin spreads out
Biology is in abietic acid, neoabietic acid, the abietic acid that comes into leaves, levopimaric acid, dehydroabietic acid, pimaric acid, isodextropimaric acid, sandaracopimaric acid
It is at least one.
5. the preparation method of rosin propynyl ester internal plasticization PVC material according to claim 2, it is characterised in that the Azide
PVC is made by PVC and sodium azide, and reaction temperature is 10 DEG C -80 DEG C, reaction time 0.1h-12h, and reaction dissolvent is nitrogen nitrogen
Dimethylformamide.
6. the preparation method of rosin propynyl ester internal plasticization PVC material according to claim 5, it is characterised in that the PVC and
The mass ratio of sodium azide is 1:(0.5-2).
7. the preparation method of rosin propynyl ester internal plasticization PVC material according to claim 5, it is characterised in that used solvent
Quality and reactant gross mass ratio be 1:(5-20).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778362A (en) * | 2020-12-28 | 2021-05-11 | 江苏大学 | Rosin-based internal plasticization PVC material and preparation method and application thereof |
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| GB656220A (en) * | 1948-12-02 | 1951-08-15 | Expanded Rubber Co Ltd | Improvements in or relating to the production of cellular materials |
| CN102311544A (en) * | 2010-07-09 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Rosinyl plasticizer and preparation method thereof |
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| CN112778362A (en) * | 2020-12-28 | 2021-05-11 | 江苏大学 | Rosin-based internal plasticization PVC material and preparation method and application thereof |
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