CN113773504A - Polyvinyl alcohol grafted polysiloxane polymer and preparation method and application thereof - Google Patents
Polyvinyl alcohol grafted polysiloxane polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of polysiloxane composite materials, and particularly relates to a polyvinyl alcohol grafted polysiloxane polymer, a preparation method and application thereof, wherein the preparation method comprises the following steps: and (3) ring-opening octamethylcyclotetrasiloxane by using a sodium polyvinyl alcohol initiator to obtain a polyvinyl alcohol grafted polysiloxane polymer with carbon as a main chain and linear polysiloxane as a side chain. The polyvinyl alcohol grafted polysiloxane polymer can be used for reducing the haze of a PET film, and can also be used for blending silicon rubber to adjust the tensile strength and flexibility of the silicon rubber, so that the application and research of the polysiloxane in the aspects of anti-reflection and haze reduction and silicon rubber performance adjustment are widened.
Description
Technical Field
The invention belongs to the field of polysiloxane composite materials, and particularly relates to a polyvinyl alcohol grafted polysiloxane polymer, and a preparation method and application thereof.
Background
The polysiloxane backbone is a polymer consisting of repeating Si-O bonds with silicon atoms attached to organic groups. Because polysiloxane has the advantages of no toxicity, good biocompatibility, good thermal stability, good low temperature resistance, low surface tension and surface energy, good flexibility, high elasticity and the like, the polysiloxane has wide application value in advanced materials such as strain sensors, coatings, biological equipment and the like. Although the raw polysiloxane rubber has certain application characteristics, the raw polysiloxane rubber also has a plurality of defects, such as low strength, low elasticity, unstable finished product state and the like, so that the raw polysiloxane rubber needs to be cured to widen the application range. After the polysiloxane is cured, the polysiloxane can be widely applied to the fields of molds, building industry, electronic industry, automobiles, ships, aviation and the like because of different raw materials, main properties and curing and forming processes.
Disclosure of Invention
The invention discloses a polyvinyl alcohol grafted polysiloxane polymer, a preparation method and application of the polyvinyl alcohol grafted polysiloxane polymer, wherein the purpose of increasing light transmittance is achieved through a phase separation region generated by a polyvinyl alcohol and polysiloxane chain segment and good light transmittance of polysiloxane, and the polyvinyl alcohol grafted polysiloxane polymer is uniformly attached to the surface of a film due to the fluidity and adsorbability of the polysiloxane, so that the effect of reducing haze is achieved, and the polyvinyl alcohol grafted polysiloxane polymer is further researched in the aspects of anti-reflection and haze reduction; the aim of adjusting the elongation of the silicone rubber is achieved through the self-structure action of the graft polymer, the toughness of the graft polymer is improved, and the research of the polyvinyl alcohol graft polysiloxane polymer on the aspect of adjusting the application performance of the silicone rubber is widened.
In order to realize the purpose of the invention, the adopted technical scheme is as follows:
a polyvinyl alcohol grafted polysiloxane copolymer having the structural formula:
The reaction equation of the preparation method of the polyvinyl alcohol grafted polysiloxane copolymer is as follows:
further, the preparation method of the polyvinyl alcohol grafted polysiloxane copolymer comprises the following steps:
(1) preparation of macroinitiator: fully stirring polyvinyl alcohol (PVA) in a dimethyl sulfoxide (DMSO) solution until the polyvinyl alcohol (PVA) is uniformly mixed, adding metal sodium, and fully stirring and reacting at the temperature of 35 +/-10 ℃ (the reaction time is preferably 2 hours) to obtain a macroinitiator (PVA-ONa) solution;
further, wherein the polyvinyl alcohol is of type 1788, 0588 and 0388; the molar ratio of hydroxyl groups to metal sodium in the polyvinyl alcohol is 1.03: 1. By changing the type and the monomer dosage of the polyvinyl alcohol, polymers with different molecular weights and reactive silicon hydroxyl groups are obtained. Of these, type 0388 is preferred because the adjustment of the molecular weight of the polyvinyl alcohol affects the amount of polysiloxane grafted onto the side chains, and the polysiloxane segment is hydrophobic, so that it can be roughly determined which type of polyvinyl alcohol can be better grafted with polysiloxane by changing the contact angle of the graft copolymer, and the test results show that type 0388 polyvinyl alcohol can be better grafted with polysiloxane because the segment is shorter and the probability of collision with monomer D4 is higher, so that more polysiloxane can be grafted.
(2) Preparation of polyvinyl alcohol graft polysiloxane copolymer: adding the macroinitiator prepared in the step (1) into octamethylcyclotetrasiloxane (D4), keeping the temperature at 60 +/-20 ℃ for reacting for 4 +/-2 hours, then stopping the reaction by using hydrochloric acid to obtain a crude product, and then washing and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer;
wherein the volume ratio of the polyvinyl alcohol sodium macroinitiator solution to the octamethylcyclotetrasiloxane is 0.5-2: 1, wherein the mass fraction of the polyvinyl alcohol macroinitiator in the polyvinyl alcohol macroinitiator solution is 1%.
Further, the washing refers to washing the crude product with absolute ethanol.
The polyvinyl alcohol grafted polysiloxane polymer is applied to coating modified PET films.
Further defined is a method for coating the modified PET film by the polyvinyl alcohol grafted polysiloxane polymer: adding the polyvinyl alcohol grafted polysiloxane copolymer into a volatile n-hexane solvent, then adding tetraethyl orthosilicate, performing ultrasonic dispersion uniformly, adding a dibutyltin dilaurate catalyst, stirring uniformly, standing for defoaming to obtain a pre-cured solution, sucking the pre-cured solution, dropwise adding the pre-cured solution onto a washed polyethylene terephthalate (PET) film, volatilizing the solvent by a spin coating method, dealcoholizing and curing at room temperature to obtain the PET film modified by coating the polyvinyl alcohol grafted polysiloxane polymer
Further, the solid content of the polyvinyl alcohol grafted polysiloxane copolymer in the normal hexane solvent is 1% -10%;
and/or the dosage of tetraethyl orthosilicate is 2-4% of the mass of the polyvinyl alcohol grafted polysiloxane copolymer;
and/or the using amount of the dibutyltin dilaurate is 0.5 percent of the mass of the polyvinyl alcohol grafted polysiloxane copolymer;
and/or the washing method of the polyethylene glycol terephthalate film comprises the steps of washing with ethanol for 1 time, washing with deionized water for 1 time, and then washing with ethanol for 1 time; the coating was carried out by means of a KW-4A bench spin coater at a speed of 1500 rpm.
The polyvinyl alcohol grafted polysiloxane polymer is applied to blending modification of silicone rubber, and the purposes of improving the elongation of the silicone rubber and improving the toughness of the silicone rubber are achieved.
Further defined, the silicone rubber blending modification method comprises the following steps: and (2) fully dispersing and dissolving the polyvinyl alcohol grafted polysiloxane copolymer and 107 glue (considering that the product needs to be dealcoholized and cured, so that the 107 glue (hydroxyl-terminated polydimethylsiloxane, the end of which contains Si-OH and can be dealcoholized and cured as the product) which can be dealcoholized and cured under the same condition) in a xylene according to a set proportion, then adding tetraethyl orthosilicate, uniformly dispersing by ultrasound, adding dibutyltin dilaurate catalyst, stirring strongly, standing for defoaming to obtain a pre-cured liquid, pouring the pre-cured liquid into a mold, vacuumizing to eliminate bubbles, dealcoholizing and curing at 50 +/-20 ℃ for 48 +/-24 h, keeping at 100 +/-20 ℃ for 2 +/-1 h, and keeping at 120 +/-10 ℃ for at least 2h to obtain the blended silicone rubber. The polyvinyl alcohol grafted polysiloxane copolymer can improve the elongation and toughness of the blended silicone rubber prepared from the polyvinyl alcohol grafted polysiloxane copolymer and 107 rubber, and improves the application range of the 107 rubber.
Further, the solid content of the polyvinyl alcohol grafted polysiloxane copolymer and 107 glue blend in the xylene solvent is 40%;
and/or the viscosity of the 107 glue is 8000 cs;
and/or the dosage of tetraethyl orthosilicate is 2 to 4 percent of the mass of the blend;
and/or the dosage of the dibutyltin dilaurate is 0.5-10% of the mass of the blend.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a polyvinyl alcohol grafted polysiloxane copolymer which has the characteristics of good stability, water resistance and medium corrosion resistance, and has good light transmittance and good fluidity of polysiloxane, meanwhile, a phase separation region is formed by polyvinyl alcohol and a polysiloxane chain segment, light can directly pass through the phase separation region to increase the light transmittance, and the good light transmittance of polysiloxane can also achieve the effect of increasing the light transmittance.
The preparation method of the polyvinyl alcohol grafted polysiloxane copolymer provided by the invention comprises the steps of firstly preparing a sodium polyvinyl alcohol macromolecular initiator, and then carrying out ring-opening polymerization to obtain a grafted polymer taking carbon as a main chain and polysiloxane as an arm. The preparation method is simple, the cost is low, and the yield can reach 60-85%.
According to the invention, the effect of increasing the light transmittance is achieved through a phase separation region generated by a polyvinyl alcohol and polysiloxane chain segment of the polyvinyl alcohol-grafted polysiloxane copolymer and the good light transmittance of polysiloxane, and the polyvinyl alcohol-grafted polysiloxane copolymer is uniformly adhered to the surface of a PET film through dealcoholization and solidification due to the fluidity and the adsorbability of polysiloxane, so that the haze of the PET film is reduced, and the polyvinyl alcohol-grafted polysiloxane polymer provided by the invention has further research on the aspects of anti-reflection and haze reduction.
The polyvinyl alcohol grafted polysiloxane copolymer is used for blending silicon rubber under the action of the structure of the polyvinyl alcohol grafted polysiloxane copolymer, can adjust the elongation of the silicon rubber and improve the toughness of the silicon rubber, and widens the research on the aspect of adjusting the application performance of the silicon rubber.
Drawings
FIG. 1 is a Fourier infrared spectrum of octamethylcyclotetrasiloxane in step (2) of example 1 and a synthesized graft polymer prepared therefrom.
FIG. 2 shows the results of the contact angle of the graft polymer prepared in step (2) of examples 1 to 9 with water with the polyvinyl alcohol graft polysiloxane copolymer prepared in step (3).
FIG. 3 is a light transmittance/haze test result of the PET film coated with the polyvinyl alcohol graft polysiloxane copolymer prepared in step (3) of examples 1-9.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is described in more detail below with reference to the following examples:
example 1
(1) Preparation of sodium polyvinyl alcohol macroinitiator
0.0301g of polyvinyl alcohol (PVA) with the model of 0388 is fully stirred in 4mL of dimethyl sulfoxide (DMSO) solution until the mixture is uniformly mixed, about 0.014g of metallic sodium is added, and the temperature is kept at 35 ℃ for fully stirring and reacting for 2h, so that the macroinitiator (PVA-ONa) solution is obtained.
(2) Preparation of polyvinyl alcohol graft polysiloxane copolymer
Mixing a polyvinyl alcohol sodium initiator and octamethylcyclotetrasiloxane in a mass ratio of 2:1, reacting at 60 +/-20 ℃ for 4 +/-2 h, stopping the reaction by hydrochloric acid, washing, and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer with the yield of 84.37 percent (experiment number 1 #).
The obtained polymerization was subjected to infrared test, and the test results are shown in FIG. 1. Curve b in FIG. 1 is 1020cm-1And 1100cm-1The double peak is the vibration absorption peak of linear Si-O-Si, which shows that D4 is successfully opened; 3442cm-1Corresponds to the stretching vibration peak of-OH, 1736cm-1Is represented by a C ═ O absorption peak at 2968cm-1Is represented by-CH3The characteristic absorption peak shows that the system contains a polyvinyl alcohol chain segment and a siloxane chain segment, which indicates that the polyvinyl alcohol grafted polysiloxane copolymer is successfully synthesized.
(3) Preparation of polyethylene terephthalate film coated with polyvinyl alcohol graft polysiloxane copolymer
0.0941g of polyvinyl alcohol grafted polysiloxane copolymer is added into 10.0228g of volatile n-hexane solvent, then 0.0866g of tetraethyl orthosilicate is added, ultrasonic dispersion is uniform, 1 drop (about 0.0153g) of dibutyltin dilaurate catalyst is added, standing and defoaming are carried out after vigorous stirring is carried out to obtain a grafted copolymer pre-curing solution, 2mL of the pre-curing solution is absorbed and dripped on a washed polyethylene terephthalate (PET) film, the solvent is volatilized through a spin coating method (1500r/min), and dealcoholization and curing are carried out at room temperature, so that the PET film coated with the polyvinyl alcohol grafted polysiloxane copolymer is obtained (experiment number 1 #).
Example 2
(1) Preparation of sodium polyvinyl alcohol macroinitiator
0.0314g polyvinyl alcohol (PVA) of type 0388 is fully stirred in 4mL dimethyl sulfoxide (DMSO) solution until being uniformly mixed, 0.014g metallic sodium is added, and the temperature is kept at 35 ℃ for fully stirring and reacting for 2h, so that the macroinitiator (PVA-ONa) solution is obtained.
(2) Preparation of polyvinyl alcohol graft polysiloxane copolymer
Mixing a polyvinyl alcohol sodium initiator and octamethylcyclotetrasiloxane in a mass ratio of 1: 1, reacting at 60 +/-20 ℃ for 4 +/-2 h, stopping the reaction by hydrochloric acid, washing, and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer with the yield of about 79.84% (experiment number 2 #).
(3) Preparation of polyethylene terephthalate film coated with polyvinyl alcohol graft polysiloxane copolymer
Adding 0.1026g of polyvinyl alcohol grafted polysiloxane copolymer into 10.1095g of volatile n-hexane solvent, then adding 0.0093g of tetraethyl orthosilicate, ultrasonically dispersing uniformly, then adding 1 drop of dibutyltin dilaurate catalyst, stirring uniformly, standing for defoaming to obtain a grafted copolymer pre-curing solution, sucking 2mL of the pre-curing solution, dripping the pre-curing solution on a washed polyethylene terephthalate (PET) film, volatilizing the solvent by a spin coating method (1500r/min), dealcoholizing and curing at room temperature to obtain the PET film coated with the polyvinyl alcohol grafted polysiloxane copolymer (experiment number 2#)*)。
Example 3
(1) Preparation of sodium polyvinyl alcohol macroinitiator
0.0306g of polyvinyl alcohol (PVA) with the model number of 0388 is fully stirred in 4mL of dimethyl sulfoxide (DMSO) solution until the polyvinyl alcohol (PVA) is uniformly mixed, 0.014g of metallic sodium is added, and the mixture is fully stirred and reacts for 2 hours at the temperature of 35 ℃ to obtain macroinitiator (PVA-ONa) solution.
(2) Preparation of polyvinyl alcohol graft polysiloxane copolymer
Mixing a polyvinyl alcohol sodium initiator and octamethylcyclotetrasiloxane in a mass ratio of 1: 2, reacting at 60 +/-20 ℃ for 4 +/-2 h, stopping the reaction by hydrochloric acid, washing, and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer, wherein the yield is about 62.76% (experiment number 3 #).
(3) Preparation of polyethylene terephthalate film coated with polyvinyl alcohol graft polysiloxane copolymer
0.1030g of polyvinyl alcohol grafted polysiloxane copolymer is added into 10.1042g of volatile n-hexane solvent, then 0.0564g of tetraethyl orthosilicate is added, ultrasonic dispersion is uniform, 1 drop of dibutyltin dilaurate catalyst is added, after intense stirring is performed, standing and defoaming are performed to obtain a grafted copolymer pre-curing solution, 2mL of the pre-curing solution is absorbed and dropped onto a washed polyethylene terephthalate (PET) film, the solvent is volatilized through a spin coating method (1500r/min), and dealcoholization and curing are performed at room temperature, so that the PET film coated with the polyvinyl alcohol grafted polysiloxane copolymer is obtained (experiment number 3 #).
(4) Preparation of blended silicone rubber
Adding 0g of polyvinyl alcohol grafted polysiloxane copolymer (prepared in the embodiment) and 5.0361g of 107 glue into 7.5482g of xylene solvent, then adding 0.1305g of tetraethyl orthosilicate, uniformly dispersing by ultrasonic, then adding 0.0606g of dibutyltin dilaurate catalyst, stirring vigorously, standing for defoaming, pouring pre-curing liquid into a mold, vacuumizing to eliminate bubbles, dealcoholizing and curing at 50 ℃ under vacuum for 24 hours, then keeping at 100 ℃ under vacuum for 1 hour, and then keeping at 130 ℃ under vacuum for 3 hours to obtain the blended silicone rubber (number 1A).
Adding 0.4569g of polyvinyl alcohol grafted polysiloxane copolymer (prepared in the embodiment) and 4.5750g of 107 glue into 7.5956g of xylene solvent, then adding 0.1018g of tetraethyl orthosilicate, ultrasonically dispersing uniformly, then adding 0.0544g of dibutyltin dilaurate catalyst, stirring uniformly, standing for defoaming, pouring the pre-cured liquid into a mold, vacuumizing to eliminate bubbles, dealcoholizing and curing at 50 ℃ for 24 hours, then keeping at 100 ℃ for 1 hour in vacuum, and keeping at 130 ℃ for 3 hours in vacuum to obtain the blended silicone rubber (number 2A).
③ 1.6719g of polyvinyl alcohol grafted polysiloxane copolymer (prepared in the example) and 3.3619g of 107 glue are added into 7.5061g of xylene solvent, then 0.1153g of tetraethyl orthosilicate are added, the mixture is dispersed uniformly by ultrasound, then 0.0531g of dibutyltin dilaurate catalyst is added, the mixture is stirred vigorously and uniformly, the mixture is kept still for defoaming, the pre-solidified solution is poured into a mold, the mold is vacuumized to eliminate bubbles, dealcoholization and solidification are carried out for 24h at 50 ℃ under vacuum, then the mixture is kept for 1h at 100 ℃ under vacuum, and then the mixture is kept for 3h at 130 ℃ under vacuum, thus obtaining the blended silicone rubber (number 3A).
3.0101g of polyvinyl alcohol grafted polysiloxane copolymer (prepared in the embodiment) and 3.0275g of 107 glue are added into 9.0564g of xylene solvent, then 0.1265g of tetraethyl orthosilicate is added, ultrasonic dispersion is uniform, 0.0720g of dibutyltin dilaurate catalyst is added, stirring is performed vigorously and uniformly, standing is performed for defoaming, the pre-cured liquid is poured into a mold, vacuumizing is performed to eliminate bubbles, dealcoholization and curing are performed for 24 hours at 50 ℃ under vacuum, then the mixture is maintained for 1 hour at 100 ℃ under vacuum, and then the mixture is maintained for 3 hours at 130 ℃ under vacuum, so that the blended silicone rubber (number 4A) is obtained.
Example 4
(1) Preparation of sodium polyvinyl alcohol macroinitiator
0.0327g of polyvinyl alcohol (PVA) with the model number of 0588 is fully stirred in 4mL of dimethyl sulfoxide (DMSO) solution until the mixture is uniformly mixed, 0.014g of metallic sodium is added, and the temperature is kept at 35 ℃ for fully stirring and reacting for 2h, so that the macroinitiator (PVA-ONa) solution is obtained.
(2) Preparation of polyvinyl alcohol graft polysiloxane copolymer
Mixing a polyvinyl alcohol sodium initiator and octamethylcyclotetrasiloxane in a mass ratio of 2:1, reacting at 60 +/-20 ℃ for 4 +/-2 h, stopping the reaction by hydrochloric acid, washing, and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer, wherein the yield is about 78.80% (experiment number 4 #).
(3) Preparation of polyethylene terephthalate film coated with polyvinyl alcohol graft polysiloxane copolymer
0.1110g of polyvinyl alcohol grafted polysiloxane copolymer is added into 9.9938g of volatile n-hexane solvent, then 0.0444g of tetraethyl orthosilicate is added, ultrasonic dispersion is uniform, 1 drop of dibutyltin dilaurate catalyst is added, after intense stirring is performed, standing and defoaming are performed to obtain a grafted copolymer pre-curing solution, 2mL of the pre-curing solution is absorbed and dropped onto a washed polyethylene terephthalate (PET) film, the solvent is volatilized through a spin coating method (1500r/min), and dealcoholization and curing are performed at room temperature, so that the PET film coated with the polyvinyl alcohol grafted polysiloxane copolymer is obtained (experiment number 4 #).
Example 5
(1) Preparation of sodium polyvinyl alcohol macroinitiator
0.0311g polyvinyl alcohol (PVA) of type 0588 is fully stirred in 4mL dimethyl sulfoxide (DMSO) solution until being mixed evenly, 0.014g metallic sodium is added, and the temperature is kept at 35 ℃ for fully stirring and reacting for 2h, thus obtaining the macroinitiator (PVA-ONa) solution.
(2) Preparation of polyvinyl alcohol graft polysiloxane copolymer
Mixing a polyvinyl alcohol sodium initiator and octamethylcyclotetrasiloxane in a mass ratio of 1: 1, reacting at 60 +/-20 ℃ for 4 +/-2 h, stopping the reaction by hydrochloric acid, washing, and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer with the yield of about 72.52% (experiment number 5 #).
(3) Preparation of polyethylene terephthalate film coated with polyvinyl alcohol graft polysiloxane copolymer
0.1130g of polyvinyl alcohol grafted polysiloxane copolymer is added into 10.0185g of volatile n-hexane solvent, then 0.0469g of tetraethyl orthosilicate is added, ultrasonic dispersion is uniform, 1 drop of dibutyltin dilaurate catalyst is added, after intense stirring is performed, standing and defoaming are performed to obtain a grafted copolymer pre-curing solution, 2mL of the pre-curing solution is absorbed and dropped onto a washed polyethylene terephthalate (PET) film, the solvent is volatilized through a spin coating method (1500r/min), and dealcoholization and curing are performed at room temperature, so that the PET film coated with the polyvinyl alcohol grafted polysiloxane copolymer is obtained (experiment number 5 #).
Example 6
(1) Preparation of sodium polyvinyl alcohol macroinitiator
0.0304g of polyvinyl alcohol (PVA) with the model number of 0588 is fully stirred in 4mL of dimethyl sulfoxide (DMSO) solution until the mixture is uniformly mixed, 0.014g of metallic sodium is added, and the temperature is kept at 35 ℃ for fully stirring and reacting for 2h, so that the macroinitiator (PVA-ONa) solution is obtained.
(2) Preparation of polyvinyl alcohol graft polysiloxane copolymer
Mixing a polyvinyl alcohol sodium initiator and octamethylcyclotetrasiloxane in a mass ratio of 1: 2, reacting at 60 +/-20 ℃ for 4 +/-2 h, stopping the reaction by using hydrochloric acid, washing, and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer, wherein the yield is about 71.47 percent (experiment number 6 #).
(3) Preparation of polyethylene terephthalate film coated with polyvinyl alcohol graft polysiloxane copolymer
0.1025g of polyvinyl alcohol grafted polysiloxane copolymer is added into 10.0344g of volatile n-hexane solvent, then 0.0343g of tetraethyl orthosilicate is added, the mixture is uniformly dispersed by ultrasonic wave, 1 drop of dibutyltin dilaurate catalyst is added, after the mixture is stirred strongly and uniformly, the mixture is kept stand and defoamed to obtain a grafted copolymer pre-curing solution, 2mL of the pre-curing solution is absorbed and dripped onto a washed polyethylene terephthalate (PET) film, the solvent is volatilized by a spin coating method (1500r/min), and dealcoholization and curing are carried out at room temperature, so that the PET film coated with the polyvinyl alcohol grafted polysiloxane copolymer is obtained (experiment number 6 #).
Example 7
(1) Preparation of sodium polyvinyl alcohol macroinitiator
0.0302g of polyvinyl alcohol (PVA) with the model of 1788 is fully stirred in 4mL of dimethyl sulfoxide (DMSO) solution until being uniformly mixed, 0.014g of metallic sodium is added, and the temperature is kept at 35 ℃ for fully stirring and reacting for 2h, so that the macroinitiator (PVA-ONa) solution is obtained.
(2) Preparation of polyvinyl alcohol graft polysiloxane copolymer
Mixing a polyvinyl alcohol sodium initiator and octamethylcyclotetrasiloxane in a mass ratio of 2:1, reacting at 60 +/-20 ℃ for 4 +/-2 h, stopping the reaction by hydrochloric acid, washing, and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer, wherein the yield is about 73.22% (experiment number 7 #).
(3) Preparation of polyethylene terephthalate film coated with polyvinyl alcohol graft polysiloxane copolymer
0.1056g of polyvinyl alcohol grafted polysiloxane copolymer is added into 10.0142g of volatile n-hexane solvent, then 0.0086g of tetraethyl orthosilicate is added, ultrasonic dispersion is uniform, 1 drop of dibutyltin dilaurate catalyst is added, after intense stirring is performed, standing and defoaming are performed to obtain a grafted copolymer pre-curing solution, 2mL of the pre-curing solution is absorbed and dropped onto a washed polyethylene terephthalate (PET) film, the solvent is volatilized through a spin coating method (1500r/min), and dealcoholization and curing are performed at room temperature, so that the PET film coated with the polyvinyl alcohol grafted polysiloxane copolymer is obtained (experiment number 7 #).
Example 8
(1) Preparation of sodium polyvinyl alcohol macroinitiator
0.0277g of polyvinyl alcohol (PVA) with the model of 1788 is fully stirred in 4mL of dimethyl sulfoxide (DMSO) solution until the mixture is uniformly mixed, 0.014g of metallic sodium is added, and the mixture is fully stirred and reacts for 2 hours at the temperature of 35 ℃ to obtain a macroinitiator (PVA-ONa) solution.
(2) Preparation of polyvinyl alcohol graft polysiloxane copolymer
Mixing a polyvinyl alcohol sodium initiator and octamethylcyclotetrasiloxane in a mass ratio of 1: 1, reacting at 60 +/-20 ℃ for 4 +/-2 h, stopping the reaction by hydrochloric acid, washing, and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer with the yield of about 62.04% (experiment number 8 #).
(3) Preparation of polyethylene terephthalate film coated with polyvinyl alcohol graft polysiloxane copolymer
0.0937g of polyvinyl alcohol grafted polysiloxane copolymer is added into 10.0104g of volatile n-hexane solvent, then 0.0516g of tetraethyl orthosilicate is added, ultrasonic dispersion is uniform, 1 drop of dibutyltin dilaurate catalyst is added, after intense stirring is uniform, standing and defoaming are carried out, a grafted copolymer pre-curing solution is obtained, 2mL of the pre-curing solution is absorbed and dropped onto a washed polyethylene terephthalate (PET) film, the solvent is volatilized through a spin coating method (1500r/min), and dealcoholization and curing are carried out at room temperature, so that the PET film coated with the polyvinyl alcohol grafted polysiloxane copolymer is obtained (experiment number 8 #).
Example 9
(1) Preparation of sodium polyvinyl alcohol macroinitiator
0.0299g of polyvinyl alcohol (PVA) with the model of 1788 is fully stirred in 4mL of dimethyl sulfoxide (DMSO) solution until the mixture is uniformly mixed, 0.014g of metallic sodium is added, and the mixture is fully stirred and reacts for 2 hours at the temperature of 35 ℃ to obtain the macroinitiator (PVA-ONa) solution.
(2) Preparation of polyvinyl alcohol graft polysiloxane copolymer
Mixing a polyvinyl alcohol sodium initiator and octamethylcyclotetrasiloxane in a mass ratio of 1: 2, reacting at 60 +/-20 ℃ for 4 +/-2 h, stopping the reaction by hydrochloric acid, washing, and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer, wherein the yield is about 66.95% (experiment number 9 #).
(3) Preparation of polyethylene terephthalate film coated with polyvinyl alcohol graft polysiloxane copolymer
0.0988g of polyvinyl alcohol grafted polysiloxane copolymer is added into 10.0105g of volatile n-hexane solvent, then 0.0394g of tetraethyl orthosilicate is added, ultrasonic dispersion is uniform, 1 drop of dibutyltin dilaurate catalyst is added, after intense stirring is performed, standing and defoaming are performed to obtain a grafted copolymer pre-curing solution, 2mL of the pre-curing solution is absorbed and dropped onto a washed polyethylene terephthalate (PET) film, the solvent is volatilized through a spin coating method (1500r/min), and dealcoholization and curing are performed at room temperature, so that the PET film coated with the polyvinyl alcohol grafted polysiloxane copolymer is obtained (experiment number 9 #).
The contact angle test (CA) was performed on the graft polymers prepared in examples 1 to 9 and the polyvinyl alcohol graft polysiloxane copolymer, and the test results are shown in FIG. 2. it can be seen from FIG. 2 that the contact angle of the water phase of the graft polymer film is reduced compared with that of the pure hydroxyl-terminated polysiloxane, probably because the hydroxyl groups of the polyvinyl alcohol side groups are not completely reacted and exhibit hydrophilicity; the hydrophobicity of the film after the product is solidified under all the proportions is improved, on one hand, the reason is that the added tetraethyl orthosilicate and hydroxyl are subjected to dealcoholization condensation reaction to form a body type cross-linking structure, the number of the hydroxyl is reduced, and the hydrophobicity is increased. On the other hand, intermolecular force between the curing films is strong, hydrophilic groups are coated, and water drops are difficult to infiltrate. The phenomenon shows that the prepared polyvinyl alcohol grafted polysiloxane copolymer has certain waterproof performance and can be applied to the field of waterproof membranes.
The transmittance/haze test of the PET films coated with the polyvinyl alcohol-grafted polysiloxane copolymer prepared in examples 1 to 9 was performed, and the results are shown in FIG. 3. it can be seen from FIG. 3 that the transmittance of the PET film coated with the polyvinyl alcohol-grafted polysiloxane copolymer is increased and the haze is decreased compared with the pure PET film. The reason for improving the light transmittance is that a phase separation region is generated by a polyvinyl alcohol chain segment and a polysiloxane chain segment, and the purpose of improving the light transmittance is achieved through the good light transmittance of the polysiloxane, and the reason for reducing the haze is that the polyvinyl alcohol grafted polysiloxane copolymer is uniformly attached to the surface of the film through the fluidity and the adsorbability of the polysiloxane. This phenomenon indicates that the prepared polyvinyl alcohol grafted polysiloxane copolymer film can be used as an anti-reflection and fog-reducing material.
The blended silicone rubber prepared in step 4 of example 3 was subjected to a swelling equilibrium method and tensile test, and the results are shown in table 1. It can be seen from Table 1 that the cross-link density of the blended silicone rubber gradually increased with the addition of the graft polymer, but the cross-link density was less than that of the pure silicone rubber. The reason why the cross-linking density of the blended silicone rubber is less than that of the pure silicone rubber may be that the addition of PVA-PDMS makes the distribution of cross-links uneven. The crosslinking density of the blended silicone rubber is increased along with the increase of the content of the PVA-PDMS, on one hand, the crosslinking bond distribution is gradually uniform, and on the other hand, the crosslinking density of the blended silicone rubber is gradually increased because the graft polymer has a plurality of active points; it can be seen from table 1 that the tensile strength of the blended silicone rubber with the compounding ratio of 10:1 is stronger, probably because the crosslinking degree at this time is favorable for the orientation arrangement and the extensional crystallization of the molecular chain. In the case of pure silicone rubber, the crosslinked network hinders the orientation of molecular chains due to its high crosslinking density, and prevents crystallization, which results in uneven stress distribution and a decrease in tensile strength. Besides the above reasons, another reason for the blended silicone rubber with other formulations is that the tensile stress distribution is not uniform due to the nonuniform distribution of the cross-linking bonds, which leads to the reduction of the tensile strength; it can also be seen from Table 1 that the elongation at break of the blended silicone rubber is greater than that of the pure silicone rubber, indicating that the addition of the graft polymer improves the flexibility of the silicone rubber. The results in Table 1 show that the graft polymer can be used for improving the tensile strength of the silicone rubber, adjusting the elongation of the silicone rubber and improving the toughness of the silicone rubber, and has application prospects in the aspect of adjusting the application performance of the silicone rubber.
TABLE 1
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
The present invention is not limited to the above embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Claims (10)
3. the method for preparing a polyvinyl alcohol-grafted polysiloxane copolymer according to claim 2, characterized in that: the method comprises the following steps:
(1) preparation of macroinitiator: fully stirring polyvinyl alcohol in a dimethyl sulfoxide solution until the polyvinyl alcohol is uniformly mixed, adding metal sodium, and keeping the temperature at 35 +/-10 ℃ for fully stirring and reacting to obtain a macromolecular initiator solution;
(2) preparation of polyvinyl alcohol graft polysiloxane copolymer: adding the macroinitiator prepared in the step (1) into octamethylcyclotetrasiloxane, reacting for 4 +/-2 hours at the temperature of 60 +/-20 ℃, stopping the reaction by hydrochloric acid, washing and drying in vacuum to obtain the polyvinyl alcohol grafted polysiloxane copolymer.
4. The method for preparing a polyvinyl alcohol-grafted polysiloxane copolymer according to claim 3, characterized in that: the polyvinyl alcohol types in the step (1) are 1788, 0588 and 0388; the molar ratio of hydroxyl groups to metal sodium in the polyvinyl alcohol is 1.03: 1;
the volume ratio of the polyvinyl alcohol sodium macroinitiator solution to the octamethylcyclotetrasiloxane in the step (2) is 0.5-2: 1, wherein the mass fraction of the polyvinyl alcohol macroinitiator in the polyvinyl alcohol macroinitiator solution is 1%;
and/or, the washing in the step (2) refers to washing the crude product by using absolute ethyl alcohol.
5. Use of a polyvinyl alcohol-grafted polysiloxane polymer according to claim 1, characterized in that: used for coating modified PET film.
6. The method for coating the modified PET film with the polyvinyl alcohol grafted polysiloxane polymer is characterized by comprising the following steps: the method comprises the following steps:
adding the polyvinyl alcohol grafted polysiloxane copolymer as claimed in claim 1 into a normal hexane solvent, then adding tetraethyl orthosilicate, ultrasonically dispersing uniformly, then adding dibutyltin dilaurate catalyst, stirring uniformly, standing for defoaming to obtain a pre-cured solution, sucking a proper amount of the pre-cured solution, dripping the pre-cured solution onto a washed polyethylene terephthalate (PET) film, volatilizing the solvent by a spin coating method, and dealcoholizing and curing at room temperature to obtain the polyvinyl alcohol grafted polysiloxane copolymer coated and modified PET film.
7. The method of claim 6, wherein the polyvinyl alcohol-grafted polysiloxane polymer is coated on the modified PET film by: the solid content of the polyvinyl alcohol grafted polysiloxane copolymer in a normal hexane solvent is 1-10%;
and/or the dosage of tetraethyl orthosilicate is 2-4% of the mass of the polyvinyl alcohol grafted polysiloxane copolymer;
and/or the using amount of the dibutyltin dilaurate is 0.5-10% of the mass of the polyvinyl alcohol grafted polysiloxane copolymer;
and/or the polyethylene glycol terephthalate film is washed by ethanol for 1 time before use, then washed by deionized water for 1 time and then washed by ethanol for 1 time; the coating was carried out by means of a KW-4A bench spin coater at a speed of 1500 rpm.
8. Use of a polyvinyl alcohol-grafted polysiloxane polymer according to claim 1, characterized in that: the method is used for blending modification of the silicone rubber.
9. The method for blending and modifying the silicone rubber by the polyvinyl alcohol grafted polysiloxane polymer is characterized by comprising the following steps: the method comprises the following steps: fully dispersing and dissolving the polyvinyl alcohol grafted polysiloxane copolymer as claimed in claim 1 and 107 glue in xylene according to a set ratio, then adding tetraethyl orthosilicate, ultrasonically dispersing uniformly, then adding dibutyltin dilaurate catalyst, stirring uniformly, standing for defoaming, pouring the pre-cured solution into a mold, vacuumizing to eliminate bubbles, dealcoholizing and curing at 50 +/-20 ℃ for 48 +/-24 hours under vacuum, then keeping at 100 +/-20 ℃ for 2 +/-1 hours under vacuum, and keeping at 120 +/-10 ℃ for at least 2 hours under vacuum to obtain the blended silicone rubber.
10. The method for modifying silicone rubber by blending polyvinyl alcohol-grafted polysiloxane polymer according to claim 9, wherein: the viscosity of the 107 glue is 8000 cs;
and/or the solid content of the polyvinyl alcohol grafted polysiloxane copolymer and 107 glue blend in the xylene solvent is 40 percent;
and/or the dosage of tetraethyl orthosilicate is 2 to 4 percent of the mass of the blend;
and/or the dosage of the dibutyltin dilaurate is 0.5-10% of the mass of the blend.
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