CN116265491A - Urea modified polyvinyl alcohol and preparation method and application thereof - Google Patents
Urea modified polyvinyl alcohol and preparation method and application thereof Download PDFInfo
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- CN116265491A CN116265491A CN202310156902.3A CN202310156902A CN116265491A CN 116265491 A CN116265491 A CN 116265491A CN 202310156902 A CN202310156902 A CN 202310156902A CN 116265491 A CN116265491 A CN 116265491A
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 174
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 174
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000004202 carbamide Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006136 alcoholysis reaction Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003814 drug Substances 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000003356 suture material Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000003337 fertilizer Substances 0.000 claims description 3
- 235000019249 food preservative Nutrition 0.000 claims description 3
- 239000005452 food preservative Substances 0.000 claims description 3
- 239000012876 carrier material Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000813 microbial effect Effects 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 18
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 208000012839 conversion disease Diseases 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical group [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 39
- 239000003054 catalyst Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000047 product Substances 0.000 description 21
- 125000003158 alcohol group Chemical group 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 239000012788 optical film Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- DBGSRZSKGVSXRK-UHFFFAOYSA-N 1-[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]-3,6-dihydro-2H-pyridine-4-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CCC(=CC1)C(=O)O DBGSRZSKGVSXRK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of polyvinyl alcohol modification, in particular to IPC C08L29, and more particularly relates to urea modified polyvinyl alcohol and a preparation method and application thereof. A urea-modified polyvinyl alcohol, comprising the components of: urea, polyvinyl alcohol. The molar ratio of urea to polyvinyl alcohol repeating units is (1-3): 1, the reaction conversion rate and the mechanical property of the product can be improved; the urea reacts with the polyvinyl alcohol under the melting condition, and then is subjected to post-treatment by water-alcohol, and no solvent is added in the reaction process, so that the conversion rate is improved, the product can reach higher purity, the safety is higher, VOC gas volatilization caused by organic solvent residues is reduced, and the biocompatibility is improved.
Description
Technical Field
The invention relates to the technical field of polyvinyl alcohol modification, in particular to IPC C08L29, and more particularly relates to urea modified polyvinyl alcohol and a preparation method and application thereof.
Background
PVA (polyvinyl alcohol) contains a large number of hydroxyl groups on molecules, and is an environment-friendly high polymer material which is water-soluble, completely biodegradable, free of static electricity, free of dust absorption and good in mechanical property. However, a large number of hydroxyl groups exist on the molecular chain of PVA, and in a wet environment, the hydroxyl groups are easy to form hydrogen bonds with water molecules, so that the aggregation state structure of PVA is changed, the barrier property and mechanical property of PVA are greatly reduced, and the polyvinyl alcohol can be modified by physics or chemistry at present.
The urea, the formamide, the water and the PVA (polyvinyl alcohol) are blended, the PVA film is prepared by a low-temperature melting method, the urea and the formamide can form more stable hydrogen bonds with hydroxyl groups on PVA molecular chains, so that the intramolecular and intermolecular hydrogen bonds of the PVA are effectively destroyed, the regularity of the PVA molecular chains is destroyed, the crystallization temperature, the melting temperature and the crystallinity are reduced, but only the hydrogen bonds formed by physical action modify the polyvinyl alcohol, and deionized water is added in the reaction process, so that the reaction efficiency is not high enough, and small molecules are easy to be separated out on the surface of the polymer.
Patent CN107540995B discloses a preparation method of stock solution for polyvinyl alcohol optical film material, which comprises the following raw materials in parts by weight: 100 parts of polyvinyl alcohol, 0.01 to 20 parts of urea, 5 to 25 parts of plasticizer, 0.001 to 0.1 part of surfactant and 0.0001 to 0.01 part of antioxidant; 1. dissolving polyvinyl alcohol to form a first solution; 2. adding urea in the first step into the first solution, mixing, and then keeping the temperature at 20-90 ℃ to form a second solution; 3. adding the surfactant and the antioxidant into the plasticizer in the first step, and mixing to form a third solution; 4. mixing the second solution in the third step with the third solution in the fourth step to form a liquid material; 5. stirring the liquid material in the fifth step mechanically and ultrasonically; and step seven, filtering the liquid material stirred in the step six to form a preparation stock solution of the polyvinyl alcohol optical film, wherein the dosage of urea is too low, and excessive plasticizer is added, so that the polyvinyl alcohol optical film is only physically plasticized, and the modification effect on the polyvinyl alcohol is probably not obvious.
Disclosure of Invention
According to the invention, the polyvinyl alcohol is modified by using urea, the modification efficiency is effectively improved by adjusting the proportion between urea and the polyvinyl alcohol components and exploring the preparation process, the colorless urea modified polyvinyl alcohol is obtained, the subsequent treatment steps are reduced, compared with unmodified PVA, the glass transition temperature and the mechanical property of the modified PVA can be effectively improved, and the water resistance of the modified PVA is improved, so that the prepared urea modified polyvinyl alcohol can be applied to the high and new technical fields of fertilizer slow-release coating, operation suture materials, drug slow-release wrapping materials, mobile phone antenna LCP films and the like.
The first aspect of the invention provides urea-modified polyvinyl alcohol, which comprises the following components: urea, polyvinyl alcohol.
The urea modified polyvinyl alcohol has a molecular structure as follows:
the polyvinyl alcohol structure is as follows:
the polyvinyl alcohol repeating unit is:
the average polymerization degree of the polyvinyl alcohol is 1000-2600, and the alcoholysis degree is 80-99%.
Preferably, the polyvinyl alcohol is at least one of PVA-1088, PVA-1099, PVA-1788, PVA-1799, PVA-2488 and PVA-2699.
Further preferably, the polyvinyl alcohol is PVA-1788, the average degree of polymerization is 1700, and the degree of alcoholysis is 88% from Jinan Weicheng engineering Co., ltd.
The molar ratio of urea to polyvinyl alcohol repeating units is (1-3): 1, the reaction conversion rate can be improved, the reactivity between amino groups in urea and hydroxyl groups of polyvinyl alcohol is lower, in order to improve the reaction conversion rate, the content of urea needs to be improved, the conversion rate is reduced due to the excessively high urea, the viscosity of a reaction system is possibly improved due to the excessively high melting point of urea, the probability of molecular collision is reduced, gelation is easily caused, and further research discovers that the molar ratio of urea to the polyvinyl alcohol repeating units is 2.5:1, the mechanical property of the product can be improved, and the amino distribution of the prepared urea modified polyvinyl alcohol is more uniform.
Preferably, the molar ratio of urea to polyvinyl alcohol repeating units is (1-3): 1.
further preferably, the molar ratio of urea to polyvinyl alcohol repeating units is 2.5:1.
the second aspect of the invention provides a process for the preparation of urea-modified polyvinyl alcohol comprising the steps of:
s1, heating urea to be molten;
s2, adding polyvinyl alcohol in batches, uniformly mixing, and reacting to obtain a urea modified polyvinyl alcohol crude product;
s3, adding deionized water to dissolve the urea modified polyvinyl alcohol crude product after the reaction is finished;
s4, adding low molecular alcohol, filtering and drying to obtain urea modified polyvinyl alcohol.
When the reaction of urea-modified polyvinyl alcohol requires the use of a solvent, on the one hand, the use of a solvent to reduce the viscosity of the system due to the higher melting point of urea and the higher viscosity of the hot melt system, and on the other hand, the solubility of the basic catalyst can also be increased, but the applicant has found that when the solvent is deionized water, the system hardly reacts, possibly with the presence of water, inhibiting the reaction of urea with secondary hydroxyl groups. Further, in the reaction process, water is tried to be distilled, so that not only can a higher conversion rate not be achieved, but also the reaction cannot be performed, and the viscosity of the system is likely to change too quickly before and after deionized water is distilled. Further researches show that the mixed solvent of the dimethylacetamide organic solvent and the deionized water is selected, or the dimethylacetamide organic solvent is singly used, so that higher conversion rate can not be achieved, the use of the dimethylacetamide can reduce the miscibility with urea and polyvinyl alcohol to a certain extent, and the collision probability between amino and hydroxyl is reduced.
In order to improve the compatibility between systems, the organic solvent N-methyl pyrrolidone with higher boiling point is selected, and the color of the product is not colorless, but yellow substances, which possibly cause side reactions between impurities in the N-methyl pyrrolidone and polyvinyl alcohol, are generated, so that the post-treatment decoloring step is increased.
Preferably, the urea-modified polyvinyl alcohol prepared is colorless.
The applicant surprisingly found that urea is firstly reacted with polyvinyl alcohol under a melting condition, then is subjected to post-treatment by water-alcohol, solvent is not added, polyvinyl alcohol is added at intervals of 4-6 batches, gelation can be avoided, meanwhile, higher conversion rate is obtained, and possibly, the urea is added in batches, so that the system viscosity is prevented from changing too fast, the more accurate regulation and control of the system viscosity are facilitated, meanwhile, the reaction rate is improved due to the fact that the solvent is not used for improving the proportion of urea, the prepared urea modified polyvinyl alcohol has better mechanical property, and further research shows that the urea modified polyvinyl alcohol prepared by a solvent-free system not only achieves higher purity, but also has higher safety, VOC gas volatilization caused by organic solvent residues is reduced, and biocompatibility is improved.
Preferably, the reaction is solvent-free.
Preferably, the polyvinyl alcohol is added in 4-6 batches, each batch being separated by a time period of 5-15 minutes.
Further preferably, the polyvinyl alcohol is added in 5 batches, each batch being separated by a time period of 7-12 minutes.
The reaction temperature is 150 ℃, so that the reaction rate can be improved, and along with the increase of the reaction temperature, the applicant finds that the too high reaction temperature is easy to cause gelation of a reaction product, so that the conversion rate is reduced, the difficulty of post-treatment is increased, and the mechanical property of the prepared urea modified polyvinyl alcohol is reduced.
Preferably, the reaction temperature is not higher than 150 ℃.
Further preferably, the reaction temperature is 150 ℃.
To further increase the reaction rate, the basic catalyst may be selected to reduce the reaction activation energy of the system, preferably an inorganic basic catalyst, possibly an organic catalyst, which is more difficult to separate in the post-treatment. The catalyst is CsOH.H 2 O has the best catalytic effect because the solubility directly determines the concentration of acid and alkali in the reaction systemAnd pH, because the catalyst has poor solubility in the system, the catalyst with stronger alkalinity is selected, the adding amount of the catalyst can be reduced under the condition of ensuring higher reaction rate, and the smaller adding amount of the catalyst is beneficial to post-treatment.
The step S2 also comprises a catalyst, wherein the catalyst is CsOH.H 2 O、Cs 2 CO 3 、Bu 4 PBr、NaOH、ZnO、CeO 2 One of them.
Preferably, the catalyst is CsOH.H 2 O。
In order to obtain urea-modified polyvinyl alcohol with different applications, a catalyst is not added, the conversion rate is possibly improved continuously along with the progress of the reaction, the mechanical property, the water solubility and the water resistance of the prepared urea-modified polyvinyl alcohol are dynamically changed, the catalyst is not added, the performance of the urea-modified polyvinyl alcohol in all aspects is more easily regulated and controlled by controlling the reaction time, meanwhile, an organic solvent is not used, the biocompatibility is improved, and the urea-modified polyvinyl alcohol can be applied to the field of food and medical use.
The third aspect of the invention provides application of urea modified polyvinyl alcohol to at least one of food preservative films, fertilizer slow-release coatings, surgical suture materials, drug slow-release coating materials, LCP films of mobile phone antennas and immobilized degradation microorganism carrier materials.
Preferably, the urea modified polyvinyl alcohol is applied to a drug slow release packaging material, a food preservative film and a surgical suture material.
The beneficial effects are that:
1. the molar ratio of urea to polyvinyl alcohol repeating units is (1-3): 1, the reaction conversion rate and the mechanical property of the product can be improved.
2. The urea reacts with the polyvinyl alcohol under the melting condition, and then is subjected to post-treatment by water-alcohol, and no solvent is added in the reaction process, so that the conversion rate is improved, the product can reach higher purity, the safety is higher, the VOC gas volatilization caused by the residual organic solvent is reduced, and the biocompatibility is improved.
3. The catalyst is CsOH.H 2 O, ensure higher reaction rateIn addition, the addition amount of the catalyst can be reduced, and the smaller addition amount of the catalyst is beneficial to post-treatment.
4. The reaction temperature is 150 ℃, so that the reaction rate can be improved, and gelation reaction is avoided.
Description of the drawings:
FIG. 1 shows the nuclear magnetic hydrogen spectrum of the product of example 2.
FIG. 2 is a nuclear magnetic resonance spectrum of the product of comparative example 1.
FIG. 3 is a nuclear magnetic resonance spectrum of the product of comparative example 2.
FIG. 4 is a nuclear magnetic resonance spectrum of the product of comparative example 3.
FIG. 5 is a nuclear magnetic resonance spectrum of the product of comparative example 4.
FIG. 6 is a nuclear magnetic resonance spectrum of the product of comparative example 5.
FIG. 7 is a nuclear magnetic resonance spectrum of the product of comparative example 6.
Examples
Example 1:
a urea-modified polyvinyl alcohol, comprising the components of: urea (CAS: 57-13-6), polyvinyl alcohol.
The urea modified polyvinyl alcohol has a molecular structure as follows:
the polyvinyl alcohol structure is as follows:
the polyvinyl alcohol repeating unit is:
the polyvinyl alcohol is of the type: PVA-1788, having an average degree of polymerization of 1700 and an alcoholysis degree of 88%, was obtained from Jinan Weichengzhi engineering Co., ltd.
The preparation of urea-modified polyvinyl alcohol comprises the following steps:
s1, heating urea (30 g,500 mmol) at 150 ℃ and slowly stirring at 50rpm until the urea is melted;
s2, adding polyvinyl alcohol (8.8 g,200mmol of repeating units) in 4 batches, adding 2.2g of the polyvinyl alcohol into each batch, slowly stirring and uniformly mixing at 50rpm for 7min, 9min and 12min at intervals, and reacting at 150 ℃ for 24h to obtain a crude product of urea modified polyvinyl alcohol;
s3, after the reaction is finished, 150mL of deionized water is added, and the urea modified polyvinyl alcohol crude product is dissolved at 80 ℃;
s4, when the temperature is reduced to 60 ℃, adding 100ml of ethanol, filtering, and vacuum drying at 60 ℃ for 24 hours (vacuum degree 100 Pa) to obtain urea modified polyvinyl alcohol.
The urea modified polyvinyl alcohol is applied to a drug slow-release packaging material.
Example 2:
a urea-modified polyvinyl alcohol, comprising the components of: urea (CAS: 57-13-6), polyvinyl alcohol, catalyst.
The urea modified polyvinyl alcohol has a molecular structure as follows:
the polyvinyl alcohol structure is as follows:
the polyvinyl alcohol repeating unit is:
the polyvinyl alcohol is of the type: PVA-1788, having an average degree of polymerization of 1700 and an alcoholysis degree of 88%, was obtained from Jinan Weichengzhi engineering Co., ltd.
The catalyst is CsOH.H 2 O(CAS：21351-79-1)。
The preparation of urea-modified polyvinyl alcohol comprises the following steps:
s1, heating urea (30 g,500 mmol) at 150 ℃ and slowly stirring at 50rpm until the urea is melted;
s2, polyvinyl alcohol (8.8 g,200mmol of repeating units) was added in 4 portions of 2.2g each, each at a distance of 7min at 50rpmSlowly stirring and mixing uniformly, and adding CsOH.H 2 O (1.68 g,10 mmol) is reacted for 45min at 150 ℃ to obtain a crude product of urea modified polyvinyl alcohol; as shown in fig. 1, a nuclear magnetic hydrogen spectrum of the reactant is shown.
S3, after the reaction is finished, 150mL of deionized water is added, and the urea modified polyvinyl alcohol crude product is dissolved at 80 ℃;
s4, adding 100ml of ethanol when the temperature is reduced to 60 ℃, filtering, and vacuum drying at 60 ℃ (vacuum degree 100 Pa)
After 24 hours, urea-modified polyvinyl alcohol is obtained.
The urea modified polyvinyl alcohol is applied to a drug slow-release packaging material.
Comparative example 1:
a urea-modified polyvinyl alcohol, comprising the components of: urea (CAS: 57-13-6), polyvinyl alcohol, catalyst, deionized water.
The urea modified polyvinyl alcohol has a molecular structure as follows:
the polyvinyl alcohol structure is as follows:
the polyvinyl alcohol repeating unit is:
the polyvinyl alcohol is of the type: PVA-1788, having an average degree of polymerization of 1700 and an alcoholysis degree of 88%, was obtained from Jinan Weichengzhi engineering Co., ltd.
The catalyst is CsOH.H 2 O(CAS：21351-79-1)。
The preparation of urea-modified polyvinyl alcohol comprises the following steps:
urea (6 g,100 mmol), polyvinyl alcohol (8.8 g,200mmol repeat unit), csOH.H 2 O(0.84g，
5 mmol), deionized water (45 g) was heated to reflux temperature and reacted for 36h. As shown in FIG. 2, the reaction was carried out at 13h,
Nuclear magnetic hydrogen spectrograms for 24h and 36h.
Comparative example 2:
a urea-modified polyvinyl alcohol, comprising the components of: urea (CAS: 57-13-6), polyvinyl alcohol, catalyst, deionized water.
The urea modified polyvinyl alcohol has a molecular structure as follows:
the polyvinyl alcohol structure is as follows:
the polyvinyl alcohol repeating unit is:
the polyvinyl alcohol is of the type: PVA-1788, having an average degree of polymerization of 1700 and an alcoholysis degree of 88%, was obtained from Jinan Weichengzhi engineering Co., ltd.
The catalyst is CsOH.H 2 O(CAS：21351-79-1)。
The preparation of urea-modified polyvinyl alcohol comprises the following steps:
urea (12 g,200 mmol), polyvinyl alcohol (8.8 g,200mmol repeat units), csOH.H 2 O (0.84 g,5 mmol) and deionized water (45 g) were heated to reflux temperature and reacted for 12h. As shown in fig. 3, a nuclear magnetic hydrogen spectrum of the reactant is shown.
Comparative example 3:
a urea-modified polyvinyl alcohol, comprising the components of: urea (CAS: 57-13-6), polyvinyl alcohol, catalyst, dimethylacetamide (CAS: 127-19-5).
The urea modified polyvinyl alcohol has a molecular structure as follows:
the polyvinyl alcohol structure is as follows:
the polyvinyl alcohol repeating unit is:
the polyvinyl alcohol is of the type: PVA-1788, having an average degree of polymerization of 1700 and an alcoholysis degree of 88%, was obtained from Jinan Weichengzhi engineering Co., ltd.
The catalyst is CsOH.H 2 O(CAS：21351-79-1)。
The preparation of urea-modified polyvinyl alcohol comprises the following steps:
polyvinyl alcohol (8.8 g,200mmol repeat units) was dissolved in dimethylacetamide (40 mL) with stirring at 50rpm at 150 ℃ under oil bath heating;
adding urea (12 g,200 mmol) and CsOH.H 2 O (1.68 g,10 mmol) for 8h; as shown in fig. 4, a nuclear magnetic hydrogen spectrum of the reactant is shown.
When the temperature is reduced to 60 ℃,100 ml of ethanol is added, and after filtration and vacuum drying (vacuum degree 100 Pa) at 60 ℃ for 24 hours,
and obtaining urea modified polyvinyl alcohol.
Comparative example 4:
a urea-modified polyvinyl alcohol, comprising the components of: urea (CAS: 57-13-6), polyvinyl alcohol, catalyst, dimethyl sulfoxide (CAS: 67-68-5).
The urea modified polyvinyl alcohol has a molecular structure as follows:
the polyvinyl alcohol structure is as follows:
the polyvinyl alcohol repeating unit is:
the polyvinyl alcohol is of the type: PVA-1788, having an average degree of polymerization of 1700 and an alcoholysis degree of 88%, was obtained from Jinan Weichengzhi engineering Co., ltd.
The catalyst is CsOH.H 2 O(CAS：21351-79-1)。
The preparation of urea-modified polyvinyl alcohol comprises the following steps:
polyvinyl alcohol (8.8 g,200mmol repeat units) was dissolved in dimethyl sulfoxide (40 mL), urea (12 g,200 mmol) with stirring at 50rpm at 150℃under oil bath heating;
adding CsOH.H 2 O (1.68 g,10 mmol) for 8h; as shown in FIG. 5, nuclear magnetic resonance hydrogen spectra of reactants 4h, 8h and 24h are shown.
When the temperature is reduced to 60 ℃,100 ml of ethanol is added, and the urea modified polyvinyl alcohol is obtained after filtration and vacuum drying (vacuum degree 100 Pa) at 60 ℃ for 24 hours.
Comparative example 5:
a urea-modified polyvinyl alcohol, comprising the components of: urea (CAS: 57-13-6), polyvinyl alcohol, catalyst, N-methylpyrrolidone (CAS: 872-50-4).
The urea modified polyvinyl alcohol has a molecular structure as follows:
the polyvinyl alcohol structure is as follows:
the polyvinyl alcohol repeating unit is:
the polyvinyl alcohol is of the type: PVA-1788, having an average degree of polymerization of 1700 and an alcoholysis degree of 88%, was obtained from Jinan Weichengzhi engineering Co., ltd.
The catalyst is CsOH.H 2 O(CAS：21351-79-1)。
The preparation of urea-modified polyvinyl alcohol comprises the following steps:
polyvinyl alcohol (8.8 g,200mmol of repeating units) was dissolved in N-methylpyrrolidone (45 g), urea (12 g,200 mmol) with stirring at 50rpm at 150℃under heating in an oil bath;
adding CsOH.H 2 O (1.68 g,10 mmol) for 8h; as shown in FIG. 6, the nuclear magnetic resonance hydrogen spectrum of reactant 8h was obtained.
When the temperature is reduced to 60 ℃,100 ml of ethanol is added, and the urea modified polyvinyl alcohol is obtained after filtration and vacuum drying (vacuum degree 100 Pa) at 60 ℃ for 24 hours.
Comparative example 6:
a urea-modified polyvinyl alcohol, comprising the components of: urea (CAS: 57-13-6), polyvinyl alcohol, catalyst, deionized water.
The urea modified polyvinyl alcohol has a molecular structure as follows:
the polyvinyl alcohol structure is as follows:
the polyvinyl alcohol repeating unit is:
the polyvinyl alcohol is of the type: PVA-1788, having an average degree of polymerization of 1700 and an alcoholysis degree of 88%, was obtained from Jinan Weichengzhi engineering Co., ltd.
The catalyst is CsOH.H 2 O(CAS：21351-79-1)。
The preparation of urea-modified polyvinyl alcohol comprises the following steps:
polyvinyl alcohol (8.8 g,200mmol of repeating units), urea (12 g,200 mmol) and CsOH.H 2 O (1.68 g,10 mmol) and deionized water (45 g) are added into a three-neck flask provided with a long-neck funnel connected with a water condenser and a mechanical stirrer, and after heating in an oil bath and stirring at 50rpm at 100 ℃, polyvinyl alcohol is dissolved and reacted for 3 hours, 43mL of water is distilled out in the reaction process, and the reaction is stopped until the reaction is completed for 4 hours; as shown in FIG. 7, the nuclear magnetic resonance hydrogen spectrum of reactant 4h was obtained.
The performance test method comprises the following steps:
the urea-modified polyvinyl alcohol obtained in examples and comparative examples was tested using the following test methods.
1. Conversion rate: the hydroxyl peak areas in the nuclear magnetic spectrogram before and after the reaction are respectively S 1 ,S 2 Conversion= (S 1 -S 2 )/S 1 X 100%. The products of example 1 with different reaction time nodes are subjected to nuclear magnetic characterization, the test results are shown in table 1, the products of example 2 and comparative examples 1-7 after the reaction is finished are subjected to nuclear magnetic characterization, and the test results are shown in table 2.
2. Tg (glass transition temperature): the Tg of the urea-modified polyvinyl alcohol was determined by heating the sample and reference from 20deg.C to 800deg.C with a heating rate of 10deg.C min-1 using a laboratory TGA thermogravimetric analyzer, and during the measurement, continuous nitrogen was required to stabilize the gaseous environment. The post-treatment tests in example 1 were performed with the different reaction time node products of example 1, and the test results are shown in table 1.
3. Tensile strength and elongation at break: the prepared urea modified polyvinyl alcohol is cut into 2cm samples with the thickness of 2.0mm, and the stretching speed is 50mm/min and the experimental temperature is 25 ℃ according to GB/T1040-2006 test of plastic stretching Property. The sample preparation test was carried out by taking the node products of different reaction times of example 1 and carrying out the post-treatment of example 1, and the test results are shown in Table 1, wherein "-" indicates that no test was carried out.
4. Water solubility: samples of urea-modified polyvinyl alcohol film were prepared, cut to 40X 40mm size, placed in 70℃water and the time required for rupture and complete dissolution was recorded, as 3 (21) means a rupture time of 3s and a complete dissolution time of 21s.
Note that: the thickness of the sample is 300 micrometers in the test, the time is recorded by a stopwatch in the test process, the sample is directly placed horizontally and immersed in water, and the sample is placed still without stirring, and the time required for breaking/complete dissolution of the sample is recorded.
5. Water resistance: at 25 ℃, flattening the urea modified polyvinyl alcohol film sample, dropping a drop of deionized water on the sample, and recording the rupture time of the film.
Note that: the sample thickness was 300 microns.
6. Product properties: the color and appearance of the product after the reaction of example 2 and comparative examples 1 to 7 were observed. The test results are shown in Table 2.
The test results are shown in Table 2, wherein the reaction conversion of comparative example 1 and comparative example 2 was 0, no product was obtained, and the product properties are indicated by "-".
Performance test results:
TABLE 1
TABLE 2
| Reaction time/h | Conversion/% | Product trait |
| Example 2 | 18 | Colorless solid product |
| Comparative example 1 | 0 | - |
| Comparative example 2 | 0 | - |
| Comparative example 3 | 5 | Pale yellow product |
| Comparative example 4 | 13 | Yellow solid product |
| Comparative example 5 | 16 | Yellow solid product |
| Comparative example 6 | 15 | Viscous mixtures, not usable |
Claims (10)
1. A urea-modified polyvinyl alcohol characterized by comprising the following components: urea, polyvinyl alcohol.
2. The urea-modified polyvinyl alcohol according to claim 1, wherein the urea-modified polyvinyl alcohol has a molecular structure of:
3. the urea-modified polyvinyl alcohol according to claim 2, characterized in that the molar ratio of urea to polyvinyl alcohol repeating units is (1-3): 1.
4. the urea-modified polyvinyl alcohol according to claim 3, wherein the polyvinyl alcohol has an average degree of polymerization of 1000 to 2600 and an alcoholysis degree of 80 to 99%.
5. The preparation of urea-modified polyvinyl alcohol according to claim 1, characterized by comprising the steps of:
s1, heating urea to be molten;
s2, adding polyvinyl alcohol in batches, uniformly mixing, and reacting to obtain a urea modified polyvinyl alcohol crude product;
s3, adding deionized water to dissolve the urea modified polyvinyl alcohol crude product after the reaction is finished;
s4, adding low molecular alcohol, filtering and drying to obtain urea modified polyvinyl alcohol.
6. The process according to claim 5, wherein the urea-modified polyvinyl alcohol obtained is colorless.
7. The process according to claim 6, wherein the reaction temperature is not higher than 150 ℃.
8. The process for preparing urea-modified polyvinyl alcohol according to claim 7, wherein the reaction is solvent-free.
9. The preparation of urea-modified polyvinyl alcohol according to claim 7 or 8, wherein the polyvinyl alcohol is added in 4-6 batches.
10. The use of urea-modified polyvinyl alcohol according to any one of claims 1-4, characterized in that it is applied to at least one of food preservative films, fertilizer slow release coatings, surgical suture materials, drug slow release coating materials, LCP films for mobile phone antennas, immobilized degradation microbial carrier materials.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1304913A (en) * | 1960-12-08 | 1962-09-28 | Kurashiki Rayon Co | Process for the preparation of nitrogen-containing polyvinyl alcohol derivatives |
| US3152102A (en) * | 1960-12-08 | 1964-10-06 | Kurashiki Rayon Co | Water-soluble polyvinyl alcohol-urea reaction products |
| US5508113A (en) * | 1994-11-18 | 1996-04-16 | Mobil Oil Corp. | PVOH-based coating composition coated polymeric film |
| CN107540995A (en) * | 2017-10-18 | 2018-01-05 | 中国石油化工集团公司 | A kind of preparation method of polyvinyl alcohol optical film material stoste |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1304913A (en) * | 1960-12-08 | 1962-09-28 | Kurashiki Rayon Co | Process for the preparation of nitrogen-containing polyvinyl alcohol derivatives |
| US3152102A (en) * | 1960-12-08 | 1964-10-06 | Kurashiki Rayon Co | Water-soluble polyvinyl alcohol-urea reaction products |
| US5508113A (en) * | 1994-11-18 | 1996-04-16 | Mobil Oil Corp. | PVOH-based coating composition coated polymeric film |
| CN107540995A (en) * | 2017-10-18 | 2018-01-05 | 中国石油化工集团公司 | A kind of preparation method of polyvinyl alcohol optical film material stoste |
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