CN101735352B - Method for synthesizing glucose modified polyvinylalcohol resin - Google Patents
Method for synthesizing glucose modified polyvinylalcohol resin Download PDFInfo
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- CN101735352B CN101735352B CN2009102488697A CN200910248869A CN101735352B CN 101735352 B CN101735352 B CN 101735352B CN 2009102488697 A CN2009102488697 A CN 2009102488697A CN 200910248869 A CN200910248869 A CN 200910248869A CN 101735352 B CN101735352 B CN 101735352B
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Abstract
The invention provides a method for synthesizing glucose modified polyvinylalcohol resin, relating to a synthesis method for a chemical material and comprising the following steps: taking gluecose and polyvinylalcohol water solution as raw materials, and obtaining a thermoplastic polyvinyl alcohol/gluecose acetalation resin product under the action of acidic catalyst after salting-out, drying and dehydrating, wherein the product has the structural formula as follows. The acetalization product prepared by the invention has the advantages of good hygroscopicity and water solubility at room temperature, enhances the application prospect thereof and broadens the application fields of polyvinyl alcohol; and the value of the softening point thereof conforms to the user performance of the thermoplastic glue.As resin has the advantages of free of methanol, safety and stability, no toxicity, no pollution, no volatilization, excellent natural degrading property and the like, the resin has important actual meanings in the aspects of recycling, reducing environment pollution, lowering production cost and the like.
Description
Technical field
The present invention relates to a kind of compound method of chemical material, particularly relate to a kind of compound method of glucose modified polyvinylalcohol resin tackiness agent.
Background technology
Z 150PH is a water-soluble polymers commonly used both at home and abroad at present.Its molecule has the hydroxyl structure of high-sequential, and molecule aggregates contains a large amount of hydrogen bonds, thereby Intermolecular Forces is strong, percent crystallinity is high, makes its melt temperature near decomposition temperature, is difficult to carry out thermoplasticity processing and uses.The acetalation of Z 150PH is widely used in industries such as tackiness agent and coating already, mainly is to adopt formaldehyde, acetaldehyde and butyraldehyde etc. to carry out acetalation with Z 150PH, and the Polyvinyl acetal thing that obtains has good wide application prospect.But along with the Polyvinyl acetal degree improves, the water-soluble remarkable decline of product.In the market use range widely cultural goods tackiness agent and family decoration tackiness agent obtain the PVF thermoplastic adhesive aqueous solution by Z 150PH and formaldehyde condensation under acidic conditions mostly, relevant document and patent are a lot.But residual formaldehyde was high after reaction was accomplished, and removed difficulty, made tackiness agent have smell, had potential safety hazard, had brought rather serious pollution to environment, and this pollution has caused global extensive concern.In order to eliminate this environmental pollution, expert both domestic and external and researcher all are being devoted to develop a kind of new type of safe environment-friendly adhesive resin with good natural degradation performance.
For meeting the market requirement, people have carried out a large amount of study on the modification to the formaldehyde polyvinyl acetal stick.Zhang Jinliu point out as reduce free formaldehyde content measure---physics aldehydes removal and chemical aldehydes removal method are arisen at the historic moment, so-called physics aldehydes removal is meant and changes the quality that 107 glue manufacturing conditions improve product; And chemical aldehydes removal is the free formaldehyde generation reaction that adds in chemical substance and the system, reaches the purpose (" polyvinyl communication " PVF reactant and industrial application thereof) of aldehydes removal; Also have some researchs in addition, like Zheng Wenzhi, discoveries such as Jiang Yanxia add an amount of acetaldehyde instead of part formaldehyde in reaction obviously improve and the free formaldehyde content reduction product performance.No matter on synthesis technique, or the glue aspect of performance all is significantly increased through the tackiness agent after the modification, and has reduced formaldehyde content, but has improved cost.Simultaneously, resin in use owing to the effect of light, heat, oxygen, enzyme, also can decompose, and release formaldehyde can be said so, as long as use formaldehyde, this influence just exists.Which kind of method all can not reach the purpose (the new prescription of " Chinese tackiness agent " preparation JSF) of complete aldehydes removal.Therefore developing aldehyde-free cement becomes inevitable trend, and people have on excellent propertys such as viscosity, bounding force, water tolerance, resistant to chemical media property the phase, and the appearance of the tackiness agent of totally nontoxic is to solve the technical problem of environmental protection and application.The Wang Yu of Sichuan University loyalty etc. also provide by lactic acid directly with Z 150PH preparation, or the method (ZL200610020448.5) of the vinol/polylactic acid graft copolymer for preparing by end-blocking POLYACTIC ACID and Z 150PH.Product can use as a kind of thermoplastics raw material of fully biodegradable, and reduces cost through adding starch blending, has good processing properties and good mechanical property, especially can directly be used for being blow molded into film.
In order to reach the standard of zero formaldehyde, help environment protection.The present invention adopts nontoxic, tasteless and not volatile glucose replaces formaldehyde and the synthetic a kind of Z 150PH of Polyvinyl acetal the contract thermoplasticity water soluble resin of glucose novel environment friendly.Glucose is nontoxic, tasteless, non-volatile, wide material sources, cost are low; And has consumption; There is the high functional group of reactive behavior---semi-acetal in its molecule; Reaction is accomplished in the after product micromolecular residual few, and has good consistency with the acetalation product, and the application performance of product not have to influence basically.Synthetic thermoplastic adhesive resin has similar application performance with traditional tackiness agent, is applicable to the bonding of timber, fiber, paper product and its recycling, all kinds of building and ornament materials etc.In addition, its do not contain formaldehyde, cost low, nontoxic, harmless, pollution-free, HUMAN HEALTH and environment protection are all had certain realistic meaning, satisfy the request for utilization of environmental-protection type adhesive fully, be a kind of new green environment protection functional high molecule material.
Summary of the invention
The object of the present invention is to provide a kind of compound method of glucose modified polyvinylalcohol resin, the acetalation product of the present invention's preparation has good water absorbability and room temperature water soluble characteristic, and the numerical value of softening temperature meets the use properties of thermoplasticity hot melt adhesive; Strengthen its application prospect, widened the Application Areas of Z 150PH.
The objective of the invention is to realize through following technical scheme:
A kind of compound method of glucose modified polyvinylalcohol resin; This method is to be raw material with glucose and polyvinyl alcohol water solution; After reaction under the acid catalyst effect; Through thermoplastic polyvinyl alcohol/glucose acetal resin product that oversalting, drying and dehydrating obtain, the skeleton symbol that constitutes this product is:
The compound method of described a kind of glucose modified polyvinylalcohol resin; Wherein polyvinyl alcohol water solution is in reactor drum; Weight part is counted in the water that 5～20 parts Z 150PH under agitation joins 95～80 parts, heat 90 ℃～95 ℃ to polyvinyl alcohol resin all dissolving obtain; Be cooled to below 80 ℃ and add glucose, adding massfraction again is total mass 1.5% catalyzer, and controlled temperature was in 80 ℃～100 ℃ reactions 1～3 hour.
The compound method of described a kind of glucose modified polyvinylalcohol resin; The glucose modified polyvinylalcohol thermoplastic resin of said preparation; But adopt a kind of nontoxic, odorlessness, non-volatile natural degradation; And the glucose with consumption replaces formaldehyde and Z 150PH a kind of resin product of acetalation synthetic under nitration mixture catalysis, and wherein the add-on of glucose is 5～45 parts of weight parts.
The compound method of described a kind of glucose modified polyvinylalcohol resin; Wherein used catalyzer is a nitration mixture; Its consumption is 1.5% of a total mass, and nitration mixture is to be that 36% concentrated hydrochloric acid and 85% SPA mix according to 1: 2～2: 1 mass ratioes by massfraction.
The compound method of described a kind of glucose modified polyvinylalcohol resin through control glucose and the suitable reaction process condition of Z 150PH, makes the degree of acetalization of Z 150PH reach 14-40%.
Advantage of the present invention and effect are:
Advantage of the present invention is a synthesizing new environmental protection resin, replaces formaldehyde and Z 150PH that acetalation takes place under acidic catalyst through adopting glucose, has avoided the harm of formaldehyde fully.Because the reactive behavior of glucose molecule is higher, the hydroxyl in the Z 150PH molecular structure preferential with the aldehyde radical reaction generation Z 150PH glucose linear polymeric polymkeric substance that contracts.Because the existence of high-hydrophilic functional group-hydroxyl also can be water-soluble even the level of response of glucose is high again, and have good water absorbability.
The Z 150PH provided by the invention resin that glucose products obtains for neutral or faint acidity, nontoxic, the tasteless transparent tackiness agent aqueous solution or the drying of saltouing that contracts.The Z 150PH field such as bonding of glucose new green environment protection resin adhesive of contracting applicable to building, house decoration and paper product.The acetalation product not only has good water-solubility and water absorbability.Glucose is as multifunctional molecule simultaneously; Also can the polyvinyl alcohol crosslinked structural molecule that reticulates have been reduced hydrophilic functional group's number under the high temperature, reduce its water-soluble and water absorbability; Improve its mechanical property, but still be a kind of resin of environment amenable fully biodegradable.
The present invention has changed the highly crystalline performance of Z 150PH through the acetalation of Z 150PH and glucose.The orderly hydroxyl structure of Z 150PH molecule camber, more hydrogen bond, stronger interaction force and crystal property, though belong to water-soluble polymer, water-soluble fully for the Z 150PH of high alcoholysis degree, need heating more than 90 ℃; The Z 150PH melt temperature is difficult to carry out thermoplasticity processing and uses near decomposition temperature in addition.The acetalation product of the present invention's preparation has good water absorbability and room temperature water soluble characteristic, and the numerical value of softening temperature meets the use properties of thermoplasticity hot melt adhesive; Strengthen its application prospect, widened the Application Areas of Z 150PH.
It is main raw material that the present invention has selected Z 150PH, mainly is based on Z 150PH and is the enough biodegradable polymkeric substance of unique certified main chain carbon-carbon bond energy, in wet environment, has under the condition that bacterium exists can resolve into water and carbonic acid gas fully in 6 months; And glucose more is prone to complete natural degradation.Through the acetalation modification of glucose, changed the aggregated structure of Z 150PH molecule, destroy the crystallinity of Z 150PH, thereby reduced the fusing point and the softening temperature of resin, improved thermally melting.
Description of drawings
Fig. 1 is the infrared spectrogram of the embodiment of the invention 1 acetal resin and Z 150PH;
Fig. 2 is the room temperature water dissolubility graphic representation of every gram Z 150PH of the present invention and acetalation product;
Fig. 3 is the water absorbability graphic representation of acetalation product under differing temps of the present invention and the humidity.
Annotate: accompanying drawing of the present invention is the functional effect synoptic diagram, literal among the figure or the unintelligible understanding that does not influence technical scheme of the present invention of numeral.
Embodiment
The reaction mechanism of glucose and Z 150PH:
The invention provides Z 150PH/glucose acetalation product, this acetalation product is made up of following repeated structural unit
For the Z 150PH/glucose acetalation product that obtains said structure; Adopt following method to experimentize: in reactor drum with the Z 150PH of water dissolution certain mass; And the glucose that adds certain mass places reaction system to stir, and glucose is solved homogeneously in the polyvinyl alcohol water solution, adds certain mass fractional an acidic catalyst then; Add the thermal control certain temperature; Make the Vilaterm alcohol and glucose that acetalation take place under the acidic catalyst effect, reaction specified time postcooling, crude product through saltout, drying obtains the purpose product.
The contract preparation method of glucose thermoplastic resin of Z 150PH provided by the invention; Be that weight part is counted in the hot water that 5～20 parts Z 150PH is dissolved in 95～80 parts; Be cooled to the glucose that adds 5～45 parts of weight parts below 80 ℃; Add the acid catalyst that massfraction is a total mass 1.5% again, controlled temperature is in 80 ℃～100 ℃ reactions 1～3 hour, the Z 150PH that can the obtain requiring/glucose acetal resin aqueous solution.The drying of cooling off then, saltout obtains the acetal resin product.
Wherein used catalyzer is a nitration mixture, and nitration mixture is to be that 36% concentrated hydrochloric acid and 85% SPA mix according to the different mass ratio by massfraction, and experiment is chosen 1: 1,1: 2 and 2: 1 three mass proportionings are carried out catalyzed reaction.
Utilize sulfuric acid-its absorbancy of carbazole method test, calculate the transformation efficiency of glucose through the glucose standard working curve.The transformation efficiency that sulfuric acid-carbazole method is measured glucose is close basically with the degree of acetalization data that adopt oxammonium hydrochloride method test PVA, participates in reaction thereby prove out glucose with the semi-acetal form, promptly every mole of glucose only with one mole of hydroxyl reaction of Z 150PH.
Water-soluble test: the acetalation product film of preparation certain specification and quality, be placed on and dry in the electric drying oven with forced convection to constant weight, put into moisture eliminator cooling, subsequent use.Put it into and place in the deionized water of certain mass under the certain temperature after the dissolving specified time, will not have dissolved acetalation product film transfer, put into moisture eliminator and cool off, the quality that weighing reduces as for drying in the electric drying oven with forced convection to constant weight.
The water absorbability test: the acetalation product film of preparation certain specification and quality, be placed on and dry in the electric drying oven with forced convection to constant weight, put into moisture eliminator cooling, subsequent use.Be placed under the condition of certain temperature, different humidity, measure the film weight of different time.
Rosin products softening temperature (ring and ball method) adopts the softening point apparatus test.
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
With 20 parts of Z 150PH (1799) and 80 parts of water, put into pressure reaction still, 90 ℃～95 ℃ stir 1～2 hour after; Z 150PH is dissolved in the water fully, is mixed with 20% polyvinyl alcohol water solution, be cooled to 80 ℃ then and add 44 parts dextrose anhydrous (mass ratio of Z 150PH, water and glucose is 1: 4: 2.2; The mol ratio of Z 150PH hydroxyl and glucose is 2: 1); The nitration mixture that adds massfraction while stirring and be system total mass 1.5% is as catalyzer, and nitration mixture is that the mass ratio of concentrated hydrochloric acid and SPA is 1: 2, treat that catalyzer is uniformly dispersed after; Rising temperature of reaction to 90 ℃; Acetalation obtained product after 2 hours, was neutralized to neutrality, promptly obtained the Z 150PH glucose modified resin adhesive aqueous solution that contracts.The drying of cooling off then, saltout obtains the acetal resin product.With the spectrogram of the ir spectra of this acetal resin and material polyethylene alcohol to such as shown in the accompanying drawing 1; Its water-soluble and hygroscopic test result is seen accompanying drawing 2 and accompanying drawing 3.Degree of acetalization according to standard method test Z 150PH is 34.3%; And the acetal resin sample of preparation has been carried out softening temperature and tensile strength performance tested, the result sees table 1.
According to embodiment 1; The mass ratio that only changes Z 150PH, water and glucose is 1: 9: 2.2; Be mixed with 10% polyvinyl alcohol water solution, the mass ratio of nitration mixture concentrated hydrochloric acid and SPA is 1: 1,80 ℃ of temperature of reaction; In 1 hour reaction times, the degree of acetalization that obtains the glucose modified resin of Z 150PH is 25.2%.And the acetal resin sample of preparation has been carried out softening temperature and tensile strength performance tested, the result sees table 1.
According to embodiment 1; The mass ratio that only changes Z 150PH, water and glucose is 1: 19: 1.44; Be mixed with 5% polyvinyl alcohol water solution, the mass ratio of nitration mixture concentrated hydrochloric acid and SPA is 1: 1,100 ℃ of temperature of reaction; In 2 hours reaction times, the degree of acetalization that obtains Z 150PH glucose thermoplastic resin is 31.5%.And the acetal resin sample of preparation has been carried out softening temperature and tensile strength performance tested, the result sees table 1.
According to embodiment 1; The mass ratio that only changes Z 150PH, water and glucose is 1: 9: 1.1; Be mixed with 10% polyvinyl alcohol water solution, the mass ratio of nitration mixture concentrated hydrochloric acid and SPA is 1: 2,100 ℃ of temperature of reaction; In 1 hour reaction times, obtaining the contract degree of acetalization of glucose modified resin of Z 150PH is 18.6%.And the acetal resin sample of preparation has been carried out softening temperature and tensile strength performance tested, the result sees table 1.
According to embodiment 1; The mass ratio that only changes Z 150PH, water and glucose is 1: 4: 1.1; Be mixed with 10% polyvinyl alcohol water solution, the mass ratio of nitration mixture concentrated hydrochloric acid and SPA is 1: 1,90 ℃ of temperature of reaction; In 3 hours reaction times, obtaining the contract degree of acetalization of glucose modified resin of Z 150PH is 22.6%.And the acetal resin sample of preparation has been carried out softening temperature and tensile strength performance tested, the result sees table 1.
Embodiment 6
According to embodiment 1; The mass ratio that only changes Z 150PH, water and glucose is 1: 4: 1.1; Be mixed with 10% polyvinyl alcohol water solution, the mass ratio of nitration mixture concentrated hydrochloric acid and SPA is 2: 1,80 ℃ of temperature of reaction; In 2 hours reaction times, obtaining the contract degree of acetalization of glucose modified resin of Z 150PH is 14.6%.And the acetal resin sample of preparation has been carried out softening temperature and tensile strength performance tested, the result sees table 1.
Embodiment 7
According to embodiment 1; The mass ratio that only changes Z 150PH, water and glucose is 1: 19: 1.44; Be mixed with 5% polyvinyl alcohol water solution, the mass ratio of nitration mixture concentrated hydrochloric acid and SPA is 1: 2,80 ℃ of temperature of reaction; In 3 hours reaction times, obtaining the contract degree of acetalization of glucose modified resin of Z 150PH is 29.7%.And the acetal resin sample of preparation has been carried out softening temperature and tensile strength performance tested, the result sees table 1.
Embodiment 8
According to embodiment 1; The mass ratio that only changes Z 150PH, water and glucose is 1: 4: 2.2; Be mixed with 10% polyvinyl alcohol water solution, the mass ratio of nitration mixture concentrated hydrochloric acid and SPA is 2: 1,100 ℃ of temperature of reaction; In 3 hours reaction times, obtaining the contract degree of acetalization of glucose modified resin of Z 150PH is 40.0%.And the acetal resin sample of preparation has been carried out softening temperature and tensile strength performance tested, the result sees table 1.
Embodiment 9
According to embodiment 1, the mass ratio that only changes Z 150PH, water and glucose is 1: 4: 1.44., being mixed with 10% polyvinyl alcohol water solution, the mass ratio of nitration mixture concentrated hydrochloric acid and SPA is 2: 1,90 ℃ of temperature of reaction, in 1 hour reaction times, obtaining the contract degree of acetalization of glucose modified resin of Z 150PH is 25.4%.And the acetal resin sample of preparation has been carried out softening temperature and tensile strength performance tested, the result sees table 1.
The degree of acetalization of subordinate list 1 acetalation product and softening temperature data
Claims (3)
1. the compound method of a glucose modified polyvinylalcohol resin; It is characterized in that this method is is raw material with glucose and polyvinyl alcohol water solution; After reaction under the acid catalyst effect; Through thermoplastic polyvinyl alcohol/glucose acetal resin product that oversalting, drying and dehydrating obtain, the skeleton symbol that constitutes this product is:
Wherein polyvinyl alcohol water solution is in reactor drum, and weight part is counted in the water that 5～20 parts Z 150PH under agitation joins 95～80 parts, heat 90 ℃～95 ℃ to polyvinyl alcohol resin all dissolving obtain; Be cooled to below 80 ℃ and add glucose, adding massfraction again is total mass 1.5% catalyzer, and controlled temperature was in 80 ℃～100 ℃ reactions 1～3 hour, and the add-on of glucose is 5～45 parts of weight parts;
Used catalyzer is a nitration mixture, and its consumption is 1.5% of a total mass, and nitration mixture is to be that 36% concentrated hydrochloric acid and 85% SPA mix according to 1: 2～2: 1 mass ratioes by massfraction.
2. the compound method of a kind of glucose modified polyvinylalcohol resin according to claim 1; The glucose modified polyvinylalcohol thermoplastic resin that it is characterized in that said preparation; But adopt a kind of nontoxic, odorlessness, non-volatile natural degradation, and the glucose with consumption replaces formaldehyde and Z 150PH a kind of resin product of acetalation synthetic under nitration mixture catalysis.
3. the compound method of a kind of glucose modified polyvinylalcohol resin according to claim 1 is characterized in that making the degree of acetalization of Z 150PH reach 14-40% through control glucose and the suitable reaction process condition of Z 150PH.
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| CN102660006A (en) * | 2012-05-05 | 2012-09-12 | 曾波 | Method for synthesizing glyoxylic acid and carbohydrate water soluble resin |
| CN104927721A (en) * | 2015-05-08 | 2015-09-23 | 南通启秀门窗有限公司 | Wooden door |
| CN107474455A (en) * | 2017-08-03 | 2017-12-15 | 安徽真信涂料有限公司 | A kind of indoor composite material for decoration |
| CN110894407B (en) * | 2019-11-26 | 2020-11-24 | 山东柯帷博伟耐火材料有限公司 | Formaldehyde-free binder and application thereof |
| CN114106498A (en) * | 2021-12-06 | 2022-03-01 | 东莞天卫电磁技术有限公司 | Nitrogen-phosphorus-free polyvinyl alcohol composite material and preparation method thereof |
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