CN111303570B - Degradable composite plasticizer modified PVA and preparation method thereof - Google Patents
Degradable composite plasticizer modified PVA and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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Abstract
The invention relates to the technical field of preparation of a composite plasticizer and modification of PVA, in particular to degradable composite plasticizer modified PVA and a preparation method thereof. 100 parts of PVA and 20-30 parts of composite plasticizer according to the mass ratio of the raw materials of the modified PVA; wherein the mass ratio of the composite plasticizer is glycerol: ɛ -cl= (15-30): (2-5). The preparation method specifically comprises the following steps: firstly, carrying out ring-opening polymerization on glycerin and ɛ -CL to obtain a composite plasticizer; dripping a composite plasticizer into PVA serving as a matrix material, uniformly mixing, standing, and obtaining mixed and swelled PVA; finally, banburying and molding to obtain the modified PVA. The existing plasticizer has the problems of complex preparation method, complex compounding, subsequent pollution and the like; the compound plasticizer blend prepared by ring-opening polymerization of glycerin and ɛ -CL does not need post-treatment and does not produce waste liquid to pollute the environment. Meanwhile, the compound plasticizer has simple formula, simple preparation method, high efficiency and degradability.
Description
Technical Field
The invention relates to the technical field of preparation of a composite plasticizer and modification of PVA, in particular to degradable composite plasticizer modified PVA and a preparation method thereof.
Background
Polyvinyl alcohol (PVA) is a nontoxic, high-barrier and biodegradable water-soluble polymer material. The composite material has excellent comprehensive performance, mechanical performance and heat resistance equivalent to those of engineering plastics and wide application range. PVA has been recognized as excellent in biodegradability, and its final decomposition product isCO 2 And H 2 O has no pollution to the environment and is an excellent environment-friendly material. PVA has been used in various fields, and particularly in food preservation, the film properties prepared by PVA are superior to those of other matrix films. PVA films have been in the leading position in the production of new films and have evolved into new food packaging materials. The PVA composite film is prepared by adopting a small-sized process, such as an impregnation method and a solution casting method. The method has certain defects of high equipment cost, large occupied area, large labor force and high cost, and reduces the productivity.
At present, the PVA composite film is prepared by adopting an extrusion blow molding process flow rarely, and has the problems that because PVA contains a large number of hydroxyl groups, a large number of hydrogen bonds are formed between molecules and in molecules, the melting point and the decomposition temperature of the PVA composite film are very close, and the PVA composite film is difficult to thermoplastic process. Therefore, a plasticizer or a stabilizer with a certain proportion is required to be added to be mixed with the PVA matrix to form a complex, so that the hydrogen bonding action between PVA molecules or in molecules is replaced, the aggregation state structure of the PVA is further controlled, the crystallinity and the melting temperature of the PVA are reduced, and finally the thermoplastic processing is realized.
The existing plasticizer preparation method is complex, generally, auxiliary agents are selected for compounding, and meanwhile, the subsequent treatment causes the problems of environmental pollution and the like, so that the plasticizer for PVA with the advantages of simple formula, no subsequent pollution, degradability and environmental friendliness is needed urgently at present, meanwhile, the crystallinity and the melting point of PVA can be reduced to achieve the purpose of modifying PVA materials, and the melting and thermoplastic molding processing of PVA are realized.
Disclosure of Invention
The invention aims to:
the invention aims to provide a PVA modified by a degradable composite plasticizer and a preparation method thereof, and aims to solve the technical problems of providing a composite plasticizer which is simple in formula, pollution-free and degradable, and the PVA is plasticized by the composite plasticizer to reduce the crystallinity and the melting point of the PVA, so that the PVA is prevented from being decomposed in molding processing. The preparation method improves the dispersion effect of the composite plasticizer in the PVA matrix material through the control of the technological process, and improves the plasticizing effect of the composite plasticizer.
The technical scheme is as follows:
a degradable composite plasticizer modified PVA comprises the following raw materials: 100 parts of PVA and 20-30 parts of composite plasticizer according to mass ratio; wherein the mass ratio of the composite plasticizer is glycerol: ɛ -cl= (15-30): (2-5).
Preferably, the raw materials include: 100 parts of PVA and 20-30 parts of composite plasticizer according to mass ratio; wherein the mass ratio of the composite plasticizer is glycerol: ɛ -cl=20: 3.
preferably, the complex plasticizer is obtained by ring opening polymerization of glycerol and ɛ -CL.
The preparation method of the degradable composite plasticizer modified PVA specifically comprises the following steps:
step one: performing ring-opening polymerization on glycerol and ɛ -CL to obtain a composite plasticizer;
step two: taking PVA as a matrix material, dripping a composite plasticizer, uniformly mixing, standing, and obtaining mixed and swelled PVA;
step three: and (5) banburying and molding to obtain the modified PVA.
Preferably, the glycerol, ɛ -CL and the catalyst are stirred at constant temperature, wherein the mass ratio of the glycerol, ɛ -CL and the catalyst is: ɛ -CL: catalyst= (15-30): (2-5): (0-0.5), introducing nitrogen while stirring, and obtaining the composite plasticizer after the reaction is finished.
Preferably, the specific preparation method of the composite plasticizer is as follows: adding glycerol, ɛ -CL and a catalyst into a three-neck flask according to a certain proportion, putting the three-neck flask into an experimental device provided with an oil bath, stirring to fully mix, introducing nitrogen into the three-neck flask, starting heating, heating the oil bath to 90 ℃, keeping the temperature of 90 ℃ and reacting for 48 hours under nitrogen protection, and stopping the reaction; taking out the obtained product to obtain the composite plasticizer.
Preferably, the second specific method comprises the following steps: stirring and heating the PVA resin in a mixer at the temperature of 85-95 ℃, gradually adding the composite plasticizer in batches, stirring for 10-30 min to enable the PVA resin composite plasticizer to be fully absorbed, then placing the PVA resin composite plasticizer in a drying box, and standing for 10-15 hours at the temperature of 85-95 ℃ to obtain the mixed and swelled PVA.
Preferably, the mixed and swelled PVA is put into an internal mixer for internal mixing and molding, and the modified PVA is obtained.
Preferably, the mixing time of banburying in the third step is 8-15 min, the rotating speed is 30-50 r/min, and the forming temperature is 150-170 ℃.
The advantages and effects:
the invention provides a preparation method of a composite plasticizer modified PVA, which has the following advantages:
1. since glycerol is a common plasticizer for modified PVA, the compound plasticizer blend prepared by ring-opening polymerization of glycerol and ɛ -CL does not need post-treatment and does not produce waste liquid to pollute the environment. Meanwhile, the compound plasticizer has simple formula, simple preparation method, high efficiency and degradability.
2. The composite plasticizer can effectively reduce the melting temperature of PVA, and avoids the non-uniformity of plasticizing and modifying the composite plasticizer and the PVA and the decomposition before melting by controlling the technological process, so that the PVA can be processed by melt molding.
3. The preparation method improves the dispersion effect of the composite plasticizer in the PVA matrix material through the control of the technological process, and improves the plasticizing effect of the composite plasticizer.
Description of the drawings:
FIG. 1 is a melting graph of PVA before and after modification.
FIG. 2 is a graph showing crystallization curves before and after modification of PVA.
FIG. 3 is a graph of IR spectrum analysis before and after PVA modification.
The specific embodiment is as follows:
the invention is further described with reference to the accompanying drawings:
example 1
In the embodiment, PVA is used as a matrix, the composite plasticizer is used as a modifier, and the PVA is firstly mixed by a mixer, then is placed still for 12 hours, and is subjected to banburying molding by an internal mixer to obtain the modified PVA.
The polyvinyl alcohol (PVA) used in this example was a commercial grade 1788 from China Petroleum and Natural gas Co., ltd. ɛ -caprolactone (ɛ -CL) is 98% pure and is manufactured by Sigma Aldrich chemical Co.
(1) The catalyst stannous octoate, glycerin and ɛ -CL are put into a three-neck round-bottom flask according to the proportion of 20:3, the mixture is stirred to be fully mixed, and meanwhile, circulating nitrogen (always filled in the whole process) is introduced into the three-neck flask to remove oxygen and moisture in the system. And (3) introducing nitrogen for 20-30 min, starting heating, heating the oil to 90 ℃, heating the oil at constant temperature for 24 hours, and stopping the reaction to obtain the composite plasticizer.
(2) And (3) mixing 20-30 parts of the composite plasticizer obtained in the step (1) with 100 parts of PVA. Adding the mixture into a mixer, mixing for 20 minutes at 90 ℃, and gradually dropwise adding the plasticizer in batches; and then placing the mixed materials into a drying box, standing at 90 ℃ for 12 hours to obtain the mixed and swelled PVA.
(3) Banburying and molding the PVA material obtained in the step (2) by adopting an internal mixer to obtain modified PVA; during banburying, the process time is 8-15 min, the rotating speed is 30-50 r/min, and the forming temperature is 150-170 ℃.
Fig. 1 is a differential scanning calorimetric analysis (DSC) melting curve, fig. 2 is a DSC crystallization curve, and it can be seen from fig. 1 and 2 that, after the PVA is plasticized by the composite plasticizer, the melting temperature (Tm) of the mixed system is 154.16 ℃, the crystallization temperature (Tc) of the composite film is 99.32 ℃, and the melting temperature drop is very obvious, and only one melting peak and crystallization peak are shown, which indicates that the plasticizing effect of the composite plasticizer and the matrix PVA is excellent.
3283cm in FIG. 3 -1 Is a characteristic peak related to hydrogen bond formation between the composite plasticizer and PVA, and is 1723cm -1 Is C=O vibration peak, 1085cm -1 C-O stretching vibration is stronger than the absorption peak of pure PVA. The composite plasticizer and PVA have good mixing effect.
The plasticizing effect of the conventional plasticizer modified PVA is obviously lower than that of the present invention, and the example of the compound plasticizer for thermoplastic processing and the method for plasticizing polyvinyl alcohol thereof in the prior art of CN1025321595A provides a melting point of 179 ℃ and a thermal decomposition temperature of 269 ℃, so that the present invention obviously reduces the melting temperature in comparison, which indicates that the plasticizing effect of the compound plasticizer and the matrix PVA is excellent.
Example 2
The degradable composite plasticizer modified PVA of the embodiment comprises 100 parts of PVA and 20 parts of composite plasticizer according to the mass ratio; wherein the mass ratio of the composite plasticizer is glycerol: ɛ -cl=3: 1.
the preparation method of the degradable composite plasticizer modified PVA comprises the following steps:
step one: performing ring-opening polymerization on glycerol and ɛ -CL to obtain a composite plasticizer;
the specific preparation method of the composite plasticizer comprises the following steps: adding glycerol and ɛ -CL into a three-neck flask according to a certain proportion, putting the three-neck flask into an experimental device provided with an oil bath, stirring to fully mix, simultaneously introducing nitrogen into the three-neck flask, starting heating, heating the oil bath to 90 ℃, keeping the temperature of 90 ℃ and reacting for 48 hours under nitrogen protection, and stopping the reaction; taking out the obtained product to obtain the composite plasticizer.
Wherein the mass ratio of the glycerin to the ɛ -CL is as follows: ɛ -cl=15: 5.
step two: taking PVA as a matrix material, dripping a composite plasticizer, uniformly mixing, standing, and obtaining mixed and swelled PVA;
the method specifically comprises the following steps: stirring and heating PVA resin in a mixer at 85 ℃, gradually adding the composite plasticizer in batches, stirring for 10min to enable the PVA resin composite plasticizer to be fully absorbed, then placing the PVA resin composite plasticizer in a drying box, standing for 10 hours at 85 ℃ to obtain mixed and swelled PVA.
Step three: and (5) banburying and molding to obtain the modified PVA.
The method specifically comprises the following steps: and (3) placing the mixed and swelled PVA into an internal mixer for internal mixing and molding to obtain the modified PVA. Wherein, the mixing time of banburying is 8min, the rotating speed is 30r/min, and the forming temperature is 150 ℃.
Example 3
The degradable composite plasticizer modified PVA of the embodiment comprises 100 parts of PVA and 30 parts of composite plasticizer according to the mass ratio; wherein the mass ratio of the composite plasticizer is glycerol: ɛ -cl=15: 1.
the preparation method of the degradable composite plasticizer modified PVA comprises the following steps:
step one: performing ring-opening polymerization on glycerol and ɛ -CL to obtain a composite plasticizer;
the specific preparation method of the composite plasticizer comprises the following steps: adding glycerol, ɛ -CL and a catalyst into a three-neck flask according to a certain proportion, putting the three-neck flask into an experimental device provided with an oil bath, stirring to fully mix, introducing nitrogen into the three-neck flask, starting heating, heating the oil bath to 90 ℃, keeping the temperature of 90 ℃ and reacting for 48 hours under nitrogen protection, and stopping the reaction; taking out the obtained product to obtain the composite plasticizer.
Wherein the mass ratio of the glycerol, ɛ -CL and the catalyst is as follows: ɛ -CL: catalyst = 30:2:0.5;
step two: taking PVA as a matrix material, dripping a composite plasticizer, uniformly mixing, standing, and obtaining mixed and swelled PVA;
the method specifically comprises the following steps: stirring and heating PVA resin in a mixer at 95 ℃, gradually adding the composite plasticizer in batches, stirring for 30min to enable the PVA resin composite plasticizer to be fully absorbed, then placing the PVA resin composite plasticizer in a drying box, standing for 15 hours at 95 ℃ to obtain mixed and swelled PVA.
Step three: and (5) banburying and molding to obtain the modified PVA.
The method specifically comprises the following steps: and (3) placing the mixed and swelled PVA into an internal mixer for internal mixing and molding to obtain the modified PVA. Wherein, the mixing time of banburying is 15min, the rotating speed is 50r/min, and the forming temperature is 170 ℃.
Example 4
The degradable composite plasticizer modified PVA of the embodiment comprises 100 parts of PVA and 20 parts of composite plasticizer according to the mass ratio; wherein the mass ratio of the composite plasticizer is glycerol: ɛ -cl=30: 5.
the preparation method of the degradable composite plasticizer modified PVA comprises the following steps:
step one: performing ring-opening polymerization on glycerol and ɛ -CL to obtain a composite plasticizer;
the specific preparation method of the composite plasticizer comprises the following steps: adding glycerol, ɛ -CL and a catalyst into a three-neck flask according to a certain proportion, putting the three-neck flask into an experimental device provided with an oil bath, stirring to fully mix, introducing nitrogen into the three-neck flask, starting heating, heating the oil bath to 90 ℃, keeping the temperature of 90 ℃ and reacting for 48 hours under nitrogen protection, and stopping the reaction; taking out the obtained product to obtain the composite plasticizer.
Wherein the mass ratio of the glycerol, ɛ -CL and the catalyst is as follows: ɛ -CL: catalyst = 30:5:0.2;
step two: taking PVA as a matrix material, dripping a composite plasticizer, uniformly mixing, standing, and obtaining mixed and swelled PVA;
the method specifically comprises the following steps: stirring and heating the PVA resin in a mixer at 90 ℃, gradually adding the composite plasticizer in batches, stirring for 20min to enable the PVA resin composite plasticizer to be fully absorbed, then placing the PVA resin composite plasticizer in a drying box, standing for 12 hours at 90 ℃, and obtaining the mixed and swelled PVA.
Step three: and (5) banburying and molding to obtain the modified PVA.
The method specifically comprises the following steps: and (3) placing the mixed and swelled PVA into an internal mixer for internal mixing and molding to obtain the modified PVA. Wherein, the mixing time of banburying is 12min, the rotating speed is 40r/min, and the forming temperature is 160 ℃.
Claims (8)
1. A degradable composite plasticizer modified PVA, characterized in that: the raw materials comprise: 100 parts of PVA and 20-30 parts of composite plasticizer according to mass ratio; wherein the mass ratio of the composite plasticizer is glycerol: ɛ -cl= (15-30): (2-5); the compound plasticizer is obtained by ring-opening polymerization of glycerin and ɛ -CL.
2. The degradable composite plasticizer modified PVA of claim 1, wherein: the raw materials comprise: 100 parts of PVA and 20-30 parts of composite plasticizer according to mass ratio; wherein the mass ratio of the composite plasticizer is glycerol: ɛ -cl=20: 3.
3. the method for preparing the degradable composite plasticizer modified PVA according to any one of claims 1-2, which is characterized by comprising the following steps: the preparation method specifically comprises the following steps:
step one: performing ring-opening polymerization on glycerol and ɛ -CL to obtain a composite plasticizer;
step two: taking PVA as a matrix material, dripping a composite plasticizer, uniformly mixing, standing, and obtaining mixed and swelled PVA;
step three: and (5) banburying and molding to obtain the modified PVA.
4. The method for preparing the degradable composite plasticizer modified PVA according to claim 3, wherein the method comprises the following steps: stirring glycerin, ɛ -CL and a catalyst at constant temperature, wherein the mass ratio of the glycerin, ɛ -CL and the catalyst is as follows: ɛ -CL: catalyst= (15-30): (2-5): (0.2-0.5), introducing nitrogen while stirring, and obtaining the composite plasticizer after the reaction is finished.
5. The method for preparing the degradable composite plasticizer modified PVA according to claim 4, wherein the method comprises the following steps: the specific preparation method of the composite plasticizer comprises the following steps: adding glycerol, ɛ -CL and a catalyst into a three-neck flask according to a certain proportion, putting the three-neck flask into an experimental device provided with an oil bath, stirring to fully mix, introducing nitrogen into the three-neck flask, starting heating, heating the oil bath to 90 ℃, keeping the temperature of 90 ℃ and reacting for 48 hours under nitrogen protection, and stopping the reaction; taking out the obtained product to obtain the composite plasticizer.
6. The method for preparing the composite plasticizer modified PVA according to claim 4, wherein the method comprises the following steps: the second specific method comprises the following steps: stirring and heating the PVA resin in a mixer at the temperature of 85-95 ℃, gradually adding the composite plasticizer in batches, stirring for 10-30 min to enable the PVA resin composite plasticizer to be fully absorbed, then placing the PVA resin composite plasticizer in a drying box, and standing for 10-15 hours at the temperature of 85-95 ℃ to obtain the mixed and swelled PVA.
7. The method for preparing the degradable composite plasticizer modified PVA according to claim 4, wherein the method comprises the following steps: and (3) placing the mixed and swelled PVA into an internal mixer for internal mixing and molding to obtain the modified PVA.
8. The method for preparing the degradable composite plasticizer modified PVA according to claim 4, wherein the method comprises the following steps: and step three, mixing time of banburying is 8-15 min, rotating speed is 30-50 r/min, and forming temperature is 150-170 ℃.
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| US5612412A (en) * | 1994-09-30 | 1997-03-18 | Daicel Chemical Industries, Ltd. | Lactone-modified polyvinyl alcohol, a process for the preparation thereof |
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