CN1054860C - Vinyl alcohol polymer - Google Patents
Vinyl alcohol polymer Download PDFInfo
- Publication number
- CN1054860C CN1054860C CN95190597A CN95190597A CN1054860C CN 1054860 C CN1054860 C CN 1054860C CN 95190597 A CN95190597 A CN 95190597A CN 95190597 A CN95190597 A CN 95190597A CN 1054860 C CN1054860 C CN 1054860C
- Authority
- CN
- China
- Prior art keywords
- vinyl alcohol
- alcohol polymer
- present
- vinyl
- pva
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention discloses a vinyl alcohol polymer provided with a hydroxyalkyl side chain containing 2 to 20 carbon atoms. Because a traditional water solubility vinyl alcohol polymer has a great amount of water solution foaming amount during high interfacial activity, the traditional water solubility vinyl alcohol polymer has problems when used for industry. Although the vinyl alcohol polymer of the present invention has the high interfacial activity under the condition of water solubility, the water solution foaming amount of the vinyl alcohol polymer is less. Thus, the present invention has excellent industrial applicability. The vinyl alcohol polymer of the present invention can be used as thermoplastic resin and a dispersion stabilizer. Additionally, the vinyl alcohol polymer of the present ivnention has various purposes, such as surface active agents with various purposes, coating agents for paper, paper modification agents of paper components and pigment binding agents, wood, paper, the adhesive of aluminum foils, inorganic materials, etc., nonwoven adhesive, paint, warp sizing agents, fiber processing auxiliary agents, hydrophobic fibre sizing agents of polyester fiber, etc., various thin films, sheet materials, bottles, fibers, etc.
Description
Technical field
The present invention relates to the vinyl alcohol polymer of good thermal stability.
Background technology
Containing the representative of the vinyl alcohol polymer of vinyl alcohol units as intramolecularly--polyvinyl alcohol (being designated hereinafter simply as " PVA ") is known.Because PVA has good film-forming properties, the transparency and intensity, therefore be widely used as the modification agent of paper, for example paper coating agent and additive; The tackiness agent of paper, timber and inorganics etc.; Warp sizing agent, film and sheet material etc.Traditional PVA is divided into " complete hydrolysis PVA ", and its degree of hydrolysis is about 98% (mole) and " partial hydrolysis PVA ", and its degree of hydrolysis is about 88% (mole).
Conventional P VA is owing to existing the bad problem of thermostability, so use with the form of the aqueous solution always.Therefore, complete hydrolysis PVA is because its fusing point, can not carry out the heat fusing shaping very near its heat decomposition temperature.On the other hand, therefore the PVA of partial hydrolysis exists the problem that produces the acetic acid smell because its fusing point is lower than complete hydrolysis PVA, and thermostability is poorer when heat fusing is shaped.
Once the someone proposed the method that the PVA heat fusing is shaped, and comprised by PVA and a kind of softening agent or other polymer blendings being reduced the melt viscosity of PVA.But in the situation of the method for adding softening agent, when moulded product used for a long time, the content of softening agent can reduce in time in the moulded product in moulded product, and the result is not enough in the flexibility of the low temperature and low humidity condition counterdie goods in winter, thereby caused cracking or be full of cracks.On the other hand, when adopting the method with PVA and other polymer blending, so because the mechanical property of both bad moulded products that obtains of consistency significantly reduces, transparency is reduction greatly also.
In addition, also the someone proposes PVA is carried out modification to reduce the fusing point of PVA.
But, contain ω-hydroxyalkyl vinyl ether unit and the unitary PVA of alkyl vinyl ether (special fair 4-10885 number) and contain the unitary PVA of polyoxyethylene mono allyl ether (special fair 5-49683 number), so there is the problem of poor heat stability owing to contain ehter bond.Contain the unitary PVA of vinyl carbinol (spy opens clear 62-229135) though its thermostability has improvement to a certain degree, on reality is used, still have the insufficient problem of thermostability, and also have the safety problem of remaining vinyl carbinol among the PVA.In addition, contain the unitary PVA of alpha-olefin (spy opens clear 63-289581), therefore exist relevant therewith melt viscosity and significantly raise and water-fast problem owing to contain hydrophobic grouping.
Disclosure of an invention
An object of the present invention is to provide a kind of new vinyl alcohol polymer of excellent heat stability.
Another object of the present invention provides a kind of new vinyl alcohol polymer, though this polymkeric substance is to have high interfacial activity under the water miscible situation at described PVA, it can provide the few aqueous solution of foam.
Owing to for addressing the above problem the result of the further investigation of carrying out, present inventors have had been found that the vinyl alcohol polymer of the hydroxyalkyl side chain of a kind of 2-20 of containing carbon atom, have finished the present invention.
Vinyl alcohol polymer of the present invention must contain vinyl alcohol units in its molecule.
The side chain of vinyl alcohol polymer of the present invention is the hydroxyalkyl that contains 2-20 carbon atom, and described side chain must be bonded directly on the main chain of this vinyl alcohol polymer.
The carbon atom number of the hydroxyalkyl in the vinyl alcohol polymer of the present invention is 2-20, better is 2-15, is more preferably 3-10.This hydroxyalkyl is an alkyl that contains at least one hydroxyl, from thermostability and water-soluble viewpoint, is good with ω-hydroxyalkyl wherein.Alkyl in the hydroxyalkyl can be the alkyl substituted alkyl of straight or branched that one of them hydrogen is contained 1-9 carbon atom.
The example that has the monomeric unit of the hydroxyalkyl that contains 2-20 carbon atom chain is the olefin unit that contains hydroxyl.From the polymerization degree that is easy to control vinyl alcohol polymer and the viewpoint that is easy to control the content that contains the hydroxyalkyl monomeric unit, preferably 3-butene-1-alcohol, 4-amylene-1-ol, 5-hexen-1-ol, 7-octen-1-ol, 9-decen-1-ol, 11-dodecylene-1-alcohol, 3-methyl-3-butene-1-alcohol etc. in described monomeric unit.Except these monomeric units, also can use the monomeric unit that contains ester group, because this monomeric unit can produce hydroxyl when the hydrolysis of vinyl acetate polymkeric substance generates vinyl alcohol polymer.
Though the content aspect for the hydroxyalkyl that contains 2-20 carbon atom in the vinyl alcohol polymer of the present invention has no particular limits, suitable content is as described below.
When vinyl alcohol polymer of the present invention used as the heat fusing shaping resin, hydroxyalkyl content was preferably 0.1-50% (mole), more preferably 1-30% (mole).
When vinyl alcohol polymer of the present invention is shaped as heat fusing and during the use of water soluble resin purposes, hydroxyalkyl content is preferably 0.3-30% (mole), more preferably 0.5-20% (mole).
When vinyl alcohol polymer of the present invention used as the dispersion stabilizer of letex polymerizations such as vinyl acetate monomer, hydroxyalkyl content was preferably 0.1-25% (mole), more preferably 0.3-15% (mole).
When hydroxyalkyl content during less than 0.1% (mole), the degree that thermostability, heat fusing plasticity and interfacial activity are improved is not enough.On the other hand, when this content surpasses 30% (mole), water-soluble can the reduction; When this content surpasses 50% (mole), the characteristic variation of vinyl alcohol polymer.
Degree of hydrolysis for vinyl alcohol polymer of the present invention is not specifically limited, no matter be complete hydrolysis or partial hydrolysis can.But from the viewpoint of thermostability and heat fusing plasticity, degree of hydrolysis better is at least 50% mole, is more preferably at least 70% mole, preferably at least 80% mole.
The viscosity average polymerization degree of vinyl alcohol polymer of the present invention (being designated hereinafter simply as " polymerization degree ") better is 100-20,000, be more preferably 200-8, and 000,300-5 preferably, 000.When the polymerization degree less than 100 the time, the characteristic variation of vinyl alcohol polymer.On the other hand, when the polymerization degree surpasses at 20,000 o'clock, then be difficult to the commercial mass production vinyl alcohol polymer.
Vinyl alcohol polymer of the present invention can comprise the olefin-copolymerization that makes vinyl acetate and contain hydroxyalkyl, then the method that resulting vinyl acetate polymkeric substance is hydrolyzed with any currently known methods production in alcohol or dimethyl sulphoxide solution.
The example of vinyl acetate has vinyl formate, vinyl acetate, propionate and valeric acid vinyl acetate, is good with vinyl acetate wherein.
Vinyl alcohol polymer of the present invention can with the vinyl unsaturated monomer copolymerization in the scope of not damaging effect of the present invention.
The example of vinyl unsaturated monomer has alkene, for example ethene, propylene, 1-butylene and iso-butylene; Unsaturated acid, for example vinylformic acid, methacrylic acid, Ba Dousuan, phthalic acid or Tetra hydro Phthalic anhydride, toxilic acid or maleic anhydride, furoate clothing or furoate clothing acid anhydride and its esters or contain the mono alkyl ester or the dialkyl of 1-18 carbon atom; Acrylic amide for example contains N-alkyl acrylamide, N,N-DMAA, 2-acrylamide propanesulfonic acid or its esters and acrylamide propyl-dimethyl amine or its acid salt or the quaternary ammonium salt of 1-18 carbon atom; The methacryloyl amine for example contains N-alkyl methyl acrylamide, the N of 1-18 carbon atom, N-dimethylmethacryl amide, 2-Methacrylamide propanesulfonic acid or its esters and dimethylaminopropyl methacrylamide or its acid salt or quaternary ammonium salt; N-vinylamide class, for example N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide; Vinyl nitrilation thing, for example vinyl cyanide and methacrylonitrile; Vinyl ether for example contains alkyl vinyl ether, hydroxyalkyl vinyl ether and the alkoxyalkyl vinyl ether of 1-18 carbon atom; Vinyl halide, for example vinylchlorid, vinylidene chloride, vinyl fluoride, vinylidene fluoride and bromine ethene; Vinyl silanes is as the trimethoxy vinyl silanes; Allylic cpd, for example allyl acetate, chlorallylene, vinyl carbinol and dimethyl vinyl carbinol; Chlorination trimethylammonium-(3-acrylamide-3-dimethyl propyl) ammonium and acrylamide-2-methyl propane sulfonic acid.
Vinyl alcohol polymer of the present invention comprises by vinyl acetate monomer such as vinyl acetate and the alkene that contains hydroxyalkyl at mercaptan, carry out copolymerization under existing as thioacetic acid or thiohydracrylic acid, then the terminal groups modification vinyl alcohol polymer that resulting multipolymer hydrolysis is made.
Vinyl acetate has mass polymerization, solution polymerization, suspension polymerization, letex polymerization and various known polymerization process with the example that closes the olefin copolymerization process of hydroxyalkyl.In these methods, what adopt usually is mass polymerization or the solution polymerization process of for example making solvent with alcohol, in order to obtain the high polymerization degree, can adopt emulsion polymerization.The example of alcohol that can be used as the solvent of solution polymerization has lower alcohol, as methyl alcohol, ethanol and propyl alcohol.The example that is used for the initiator of copolymerization is known azo-compound or superoxide, α for example, α '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), benzoyl peroxide and percarbonic acid n-propyl.Though be not particularly limited, be suitable from the scope of room temperature to 150 ℃ for polymerization temperature.
When vinyl acetate is dissolved in the alcohol with the multipolymer that contains the alkene of hydroxyalkyl, or hydrolysis just takes place when being dissolved in the aqueous alcohol under some occasion.Lower alcohol all is applicable to this purpose as methyl alcohol and ethanol etc., is good with methyl alcohol especially.The alcohol that is used for hydrolysis reaction can contain the solvent that is no more than 40% (weight), as acetone, methyl acetate, ethyl acetate and benzene etc.The catalyzer that can be used for hydrolysis reaction is an alkali metal hydroxide, as potassium hydroxide and sodium hydroxide, and alkaline catalysts such as sodium methylate and acid catalyst such as mineral acid.Though the temperature for hydrolysis reaction is not particularly limited, 20-60 ℃ temperature range is suitable.When being settled out gluey product in the hydrolytic process, just this product is taken out, pulverizes, and carry out drying, so just obtained vinyl alcohol polymer of the present invention.
Vinyl alcohol polymer of the present invention is compared with traditional PVA has extremely excellent thermostability.That is to say, the thermal stability index of vinyl alcohol polymer of the present invention, promptly the polymer weight temperature that reduces at 5% o'clock (hereinafter referred to as " 5% weight reduces temperature ") is higher than 300 ℃.Though thermoplastic resin such as polyolefine can carry out that heat fusing is shaped in the temperature that is not higher than 250 ℃ with technical scale, consider long-term operation, actual heat fusing forming temperature must be set in and reduce temperature than 5% weight and hang down 50 ℃ temperature at least.Therefore, its 5% weight reduces vinyl alcohol polymer of the present invention that temperature is higher than 300 ℃ and can be described as and have excellent plant-scale heat fusing plasticity.Vinyl alcohol polymer of the present invention also has good thermostability, specifically, also can at high temperature carry out melt-shaping under the situation of low in hydrolysis degree or partial hydrolysis PVA.
Reason is not fully aware of qualitatively though vinyl alcohol polymer of the present invention demonstrates excellent heat, can infer that this is because due to side chain (hydroxyalkyl that contains 2-20 carbon atom) is bonded directly on the vinyl alcohol polymer main chain.
In order further to improve the heat fusing plasticity, also can add softening agent in the vinyl alcohol polymer of the present invention.The example that is applicable to the softening agent of this purposes has, but be not limited to glycols, be not more than 600 polyoxyethylene glycol, trimethylene, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol and propylene glycol as ethylene glycol, glycol ether, triglycol, Tetraglycol 99, molecular weight; Glycerine; Dibasic alcohol, as 1,3 butylene glycol and 2, the 3-butyleneglycol; TriMethylolPropane(TMP); Glycerol dimer; The 3-methyl isophthalic acid, 3,5-penta triol, the water of a small amount of (below 20%) etc.In 100 parts by weight of ethylene alkoxide polymers is benchmark, and the addition of softening agent better is no more than 30 weight parts, better is no more than 20 weight parts, especially is no more than 10 weight parts.
Vinyl alcohol polymer of the present invention can be low with reactivity inorganic materials, mix as clay, inorganic salt and glass etc. and to use.The example of inorganic materials has kaolin, clay, talcum, acid clay, silica, aluminum oxide, diatomite, wilkinite, polynite, knaur clay, frog order clay, agalmatolite, alunite, potter's clay, feldspar, asbestos, perlite, lime carbonate, magnesium hydroxide, carbon black, titanium dioxide, mica, Shirasu, glass, glass fibre etc.The median size of inorganic materials used in the present invention has no particular limits, but better is 0.1-100 μ m.
The addition of inorganic materials for 100 parts by weight of ethylene alkoxide polymers, better is no more than 2000 weight parts, better is no more than 1000 weight parts.
The manufacturing process of vinyl alcohol polymer of the present invention for example has from the solution form the solvent such as water or dimethyl sulfoxide (DMSO) to be shaped, and makes it to plastify be shaped (for example extrusion molding, injection moulding, tubular film moulding method, compression moulding and blow molding) by heating.Can obtain the moulded product of arbitrary shape, for example film, sheet material, tubing and bottle with these methods.
When vinyl alcohol polymer of the present invention was water miscible situation, although this polymkeric substance has high interfacial activity, the one-tenth of its aqueous solution bubble property was very little.Though its reason is not really clear, can infer that this is because due to side chain (hydroxyalkyl that contains 2-20 carbon atom) is bonded directly on the main chain.
Vinyl alcohol polymer of the present invention is owing to have very excellent interfacial activity, and the aqueous solution bubble few, so can be used as dispersion stabilizer, coating agent, sizing agent, tackiness agent etc.
Describe the present invention in detail with example and comparative example below.In below the example and comparative example, " part " and " % " is meant " weight part " and " weight % ", except as otherwise noted.
The content 270MHz of hydroxyalkyl side chain, vinyl acetate unit, vinyl alcohol units and other monomeric units in the vinyl alcohol polymer
1The H-NMR assay determination.Be used for
1The solvent of the vinyl alcohol polymer that H-NMR analyzes is deuterate DMSO.
The polymerization degree of vinyl alcohol polymer, water-soluble, thermostability, surface tension and 4% viscosity in aqueous solution are measured with following method.
(1) viscometric degree of polymerization:
Under the situation of degree of hydrolysis less than 99.5%, earlier with the PVA hydrolysis to degree of hydrolysis more than 99.5%, in water, measure its limiting viscosities [η] (g/dl) in 30 ℃ then, use following formula to obtain viscometric degree of polymerization (P) again from [η]:
P＝([η]×10
3/8.29)
(1/0.62)
(2) water-soluble
Preparation concentration is 10% the aqueous solution, and uses the appearance method evaluation, and its result represents with following mark:
Zero: water-soluble
*: water insoluble
(3) thermostability
Under nitrogen atmosphere, rising to 10 ℃/minute heat-up rate under 700 ℃ the condition, more than 5 hours and the refining PVA that obtains carries out TG-DTA (differential thermal analysis) test, obtaining 5% weight and reduce temperature 105 ℃ of vacuum-dryings.
(4) surface tension:
The preparation 0.3%PVA aqueous solution makes it leave standstill 60 minutes at 20 ℃, uses Wilhelmy slide method (Wilhemely plate method) to measure surface tension then.
(5) 4% solution viscosities:
The PVA aqueous solution of preparation 4% is measured Type B (Brookfield) viscosity at 20 ℃.
(6) foaminess of the aqueous solution:
Prepare 20 ℃ the 4%PVA aqueous solution, it be circulated in the vertical Glass tubing (internal diameter 4.5cm, high 150cm), make solution height reach 20cm, use then pump with 1.5 liters/minute flow with this solution circulated 15 minutes (extract out from the pipe end, return the pipe top).Measure the foam height that is produced then.Its result represents with following mark:
◎: the foam height of generation below 49cm,
Zero: the foam height of generation is 50-74cm,
△: the foam height of generation is 75-99cm,
*: the foam height of generation is more than 100cm.
Example 1
In 3 liters of polymeric kettles of opening for feed that reflux exchanger, agitator, thermometer, nitrogen ingress pipe and back interpolation usefulness are housed and pump, add 1680g vinyl acetate, 350g 7-octen-1-ol and 420g methyl alcohol.Stir and the nitrogen gas stream protection under with mixture heating up, adding 26g α when reaching 60 ℃ of constant temperature, α '-Diisopropyl azodicarboxylate (below be designated as " AIBN ") is with initiated polymerization.Proceed polymerization, constantly analyze solid contents in the polymerization reactor simultaneously, polyreaction is stopped reactor cooling after 4 hours.Transformation efficiency before polymerization stops is 59%.Resulting polymkeric substance pasty state thing is splashed in the normal hexane, make polymer precipitation.Polymkeric substance is dissolved in acetone carrying out comprising for three times then, in normal hexane after reppd redeposition-purification operations again with polymer dissolution in acetone, gained solution splashes in the distilled water, after boil-off, carry out drying, obtain purified Vinyl Acetate Copolymer (hereinafter referred to as " PVAc ") at 60 ℃.Preparation concentration is the methanol solution of 30% refining PVAc, with its stirring, adds 10% sodium hydrate methanol solution (mol ratio with respect to PVAc is 0.10) under 40 ℃, is hydrolyzed 60 minutes.The gained gelling material is pulverized, be immersed in the methyl alcohol, add 10% sodium hydrate methanol solution (mol ratio with respect to PVAc is 0.02), be hydrolyzed again 5 hours.Gained PVA methanol wash obtains white powder PVA 50 ℃ of dryings after 18 hours.7-octen-1-ol unit content among the resulting PVA is 4.5 moles of %.Basic structure and the physical properties of this PVA are shown in table 2 and table 3.
Example 2
Use 5 liters polymeric kettle, carry out following polyreaction by example 1 same method.Add 2,800g vinyl acetate between to for plastic, 300g 7-octen-1-ol, 700g methyl alcohol.Under stirring and nitrogen gas stream protection,, add 33g AIBN when reaching 60 ℃ of constant temperature with initiated polymerization with mixture heating up.4.5 after hour, transformation efficiency reaches at 63% o'clock stops polyreaction.Press example 1 same quadrat method, make refining PVAc, be hydrolyzed then, make with extra care, obtain refining PVA at last.The unitary content of 7-octen-1-ol is 8.4 moles of % among the gained PVA.Basic structure and the physical properties of this PVA are shown in table 2 and table 3.
Example 3-8
Except that polymerizing condition press shown in the table 1 change, all the other carry out polymerization, hydrolysis and refining by example 1 with quadrat method, obtain refining PVA.The basic structure of this PVA and rerum natura are shown sublist 2 and table 3.
Example 9
Use 5 liters polymeric kettle, carry out following polyreaction by example 2 same methods.Add 2,800g vinyl acetate between to for plastic, 800g 7-octen-1-ol, 30g sodium allyl sulfonate.Under stirring and hydrogen stream protection,, add 30gAIBN when reaching 60 ℃ of constant temperature with initiated polymerization with mixture heating up.Polyreaction is stopped.Make refining PVAc by example 1 with quadrat method, be hydrolyzed then, make with extra care, obtain refining PVA at last.7-octen-1-ol unit content is 11.0 moles of % among the gained PVA.Sodium allyl sulfonate unit content is 0.5 mole of %.Basic structure and the rerum natura of this PVA are shown in table 2 and table 3.
Example 10
The methanol solution (mol ratio with respect to PVAc is 0.009) that contains adding 10% sodium hydroxide among 10.2 moles of unitary PVAc of %5-hexen-1-ol that obtains in example 4 is hydrolyzed.Resulting gelling material is pulverized, used methanol wash, obtain white powder PVA after 18 hours 50 ℃ of dryings.Basic structure and the rerum natura of this PVA are shown in table 2 and table 3.
Example 11
The methanol solution (mol ratio with respect to PVAc is 0.009) that contains adding 10% sodium hydroxide among 4.5 moles of unitary PVAc of %7-octen-1-ol that obtains in example 1 is hydrolyzed.Resulting gelling material is pulverized, used methanol wash, obtain white powder PVA after 18 hours 50 ℃ of dryings.Basic structure and the rerum natura of this PVA are shown in table 2 and table 3.
Table 1
| Polymerizing condition | ||||||
| Vinyl acetate between to for plastic (g) | The monomer (g) that contains hydroxyalkyl | コモノマ- (g) | メノ-ル (g) | AIBN polymerization time (g) (hour) | Transformation efficiency (%) | |
| Embodiment 3 | 930 | 3-butene-1-alcohol 180 | 0 | 0 | 26 5.0 | 32 |
| Embodiment 4 | 930 | 5-hexen-1-ol 105 | 0 | 0 | 9 6.0 | 24 |
| Embodiment 5 | 2800 | 7-octen-1-ol 60 | 0 | 0 | 2.8 4.5 | 40 |
| Embodiment 6 | 2800 | 3-butene-1-alcohol 108 | 0 | 700 | 28 5.5 | 60 |
| Embodiment 7 | 2800 | 5-hexene-1,2-glycol 170 | 0 | 700 | 29 4.2 | 54 |
| Embodiment 8 | 1680 | 7-octene-1-acetic ester 370 | 0 | 420 | 24 3.9 | 62 |
Table 2
| The structure of PVA | ||||||
| Vinyl acetate between to for plastic unit (mole %) | Vinyl alcohol units (mole %) | The monomeric unit (mole %) that contains hydroxyalkyl | Comonomer unit (mole %) | The polymerization degree | Degree of hydrolysis (mole %) | |
| Embodiment 1 | 0.4 | 95.1 | 7-octen-1-ol 4.5 | 0 | 590 | 99.6 |
| Embodiment 2 | 0.5 | 91.1 | 7-octen-1-ol 8.4 | 0 | 510 | 99.5 |
| Embodiment 3 | 0.7 | 71.6 | 3-butene-1-alcohol 27.7 | 0 | 1500 | 99.0 |
| Embodiment 4 | 0.6 | 89.2 | 5-hexen-1-ol 10.2 | 0 | 1560 | 99.3 |
| Embodiment 5 | 0.5 | 97.9 | 7-octen-1-ol 1.6 | 0 | 1740 | 99.5 |
| Embodiment 6 | 0.5 | 93.9 | 3-butene-1-alcohol 5.6 | 0 | 550 | 99.5 |
| Embodiment 7 | 0.5 | 94.6 | 5-hexene-1,2-glycol 4.9 | 0 | 710 | 99.5 |
| Embodiment 8 | 0.1 | 95.3 | 7-octene-1-acetic ester 4.6 | 0 | 640 | 99.9 |
| Embodiment 9 | 0.3 | 88.2 | 7-octen-1-ol 11.0 | SAS 1) 0.5 | 480 | 99.7 |
| Embodiment 10 | 10.6 | 79.2 | 5-hexen-1-ol 10.2 | 0 | 1560 | 88.2 |
| Embodiment 11 | 10.1 | 85.4 | 7-octen-1-ol 4.5 | 0 | 590 | 89.4 |
1) SAS: sodium allyl sulfonate
Table 3
| The rerum natura of PVA | |||||
| Water-soluble | Thermostability (℃) | Surface tension (dyne/cm) | Solution viscosity (mPa.s) | The foaminess of the aqueous solution | |
| Embodiment 1 | ○ | 350 | 54.0 | 6.5 | ◎ |
| Embodiment 2 | ○ | 360 | 51.4 | 6.1 | ◎ |
| Embodiment 3 | ○ | 350 | 60.1 | 26.9 | ◎ |
| Embodiment 4 | ○ | 355 | 54.9 | 29.3 | ◎ |
| Embodiment 5 | ○ | 345 | 56.5 | 30.9 | ◎ |
| Embodiment 6 | ○ | 350 | 59.2 | 5.7 | ◎ |
| Embodiment 7 | ○ | 325 | 51.1 | 15.3 | ◎ |
| Embodiment 8 | ○ | 350 | 53.9 | 6.6 | ◎ |
| Embodiment 9 | ○ | 320 | 49.3 | 6.2 | ◎ |
| Embodiment 10 | ○ | 335 | 44.6 | 27.9 | ◎ |
| Embodiment 11 | × | 335 | - 1) | - 1) | - 1) |
1) owing to water insoluble, can't measure
Comparative example 1-10
Estimate by the PVAs shown in the same method his-and-hers watches 4 of example 1.It the results are shown in table 5.
Table 4
| The structure of PVA | ||||||
| Vinyl acetate between to for plastic unit (mole %) | Vinyl alcohol units (mole %) | The monomeric unit (mole %) that contains hydroxyalkyl | Comonomer unit (mole %) | The polymerization degree | Degree of hydrolysis (mole %) | |
| Comparative example 1 | 1.6 | 98.4 | - 0 | - 0 | 510 | 98.4 |
| Comparative example 2 | 26.9 | 73.1 | - 0 | - 0 | 490 | 73.1 |
| Comparative example 3 | 11.7 | 88.3 | - 0 | - 0 | 1740 | 88.3 |
| Comparative example 4 | 1.3 | 97.8 | - 0 | HBVE 1)0.6 SVE 2)0.3 | 1400 | 98.7 |
| Comparative example 5 | 0.5 | 94.8 | - 0 | Vinyl carbinol 4.7 | 570 | 99.5 |
| Comparative example 6 | 13.4 | 86.1 | - 0 | 1-dodecylene 1.0 | 1800 5) | 85.5 |
| Comparative example 7 | 0.5 | 98.6 | - 0 | POE 3) 0.9 | 1040 | 99.5 |
| Comparative example 8 | 0.5 | 97.5 | - 0 | Furoate clothing 2.0 | 1640 | 99.5 |
| Comparative example 9 | 11.3 | 88.2 | - 0 | SAS 4) 0.5 | 520 | 88.6 |
| Comparative example 10 | 1.0 | 96.0 | - 0 | バ-サ チ Star Network 3.0 sour PVC ニ Le | 1750 6) | 99.0 |
1) HBVE: ω-hydroxy butyl vinyl ether
2) SVE: stearyl vinyl ether
3) POE: polyoxyethylene (n=9) mono allyl ether
4) SAS: sodium allyl sulfonate
5) because PVA is water insoluble, so be from the PVA value that obtains of the limiting viscosity of 30 ℃ of acetone solns of acetylize gained PVAc again.
Table 5
| The rerum natura of PVA | |||||
| Water-soluble | Thermostability (℃) | Surface tension (dyne/cm) | Solution viscosity (mPa.s) | The foaminess of the aqueous solution | |
| Comparative example 1 | ○ | 260 | 63.1 | 5.5 | ◎ |
| Comparative example 2 | ○ | 220 | 42.6 | 4.6 | △ |
| Comparative example 3 | ○ | 240 | 54.9 | 22.4 | × |
| Comparative example 4 | ○ | 250 | 57.5 | 2700 | × |
| Comparative example 5 | ○ | 280 | 61.8 | 2.8 | ○ |
| Comparative example 6 | × | 290 | - 1) | - 1) | - 1) |
| Comparative example 7 | ○ | 240 | 63.2 | 15.4 | ○ |
| Comparative example 8 | ○ | 210 | 64.4 | 24.9 | ○ |
| Comparative example 9 | ○ | 230 | 56.9 | 6.5 | × |
| Comparative example 10 | × | 260 | - 1) | - 1) | - 1) |
1) owing to water insoluble, can't measure
Industrial practicality
5% weight of vinyl alcohol polymer of the present invention reduces temperature and is higher than 300 ℃, thereby has excellent thermostability.
Traditional water-soluble ethylene alkoxide polymer since interfacial activity when high its aqueous solution gas release many, therefore when industrial use, have problems, although and vinyl alcohol polymer of the present invention interfacial activity height under water-soluble situation, but the gas release of its aqueous solution is few, therefore has excellent industrial applicibility.
Vinyl alcohol polymer of the present invention can be used as thermoplastic resin and dispersion stabilizer.In addition, vinyl alcohol polymer of the present invention can be used for various uses, and for example the tensio-active agent of various uses, paper are with the coating agent, such as sizing agent, various film and sheet material, bottle and the fiber etc. of the paper of paper with composition and pigment binding agent with hydrophobic fibres such as the tackiness agent of the tackiness agent of modification agent, timber, paper, aluminium foil and inorganic materials etc., non-woven, coating, warp sizing agent, fiber process auxiliary agent, trevira.
Claims (2)
1. vinyl alcohol polymer, the viscosity average polymerization degree of described polymkeric substance is 100-20,000, and contain a side chain, and described side chain is to be bonded directly on the main chain of described polymkeric substance, the chemical formula of described side chain (1) is as follows,
-CH
2-CH
2In-R (1) formula,
R is that carbonatoms is the hydroxyalkyl of 1-8.
2. vinyl alcohol polymer according to claim 1, wherein, described hydroxyalkyl is ω-hydroxyalkyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95190597A CN1054860C (en) | 1995-06-05 | 1995-06-05 | Vinyl alcohol polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95190597A CN1054860C (en) | 1995-06-05 | 1995-06-05 | Vinyl alcohol polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1154120A CN1154120A (en) | 1997-07-09 |
| CN1054860C true CN1054860C (en) | 2000-07-26 |
Family
ID=5082515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95190597A Expired - Fee Related CN1054860C (en) | 1995-06-05 | 1995-06-05 | Vinyl alcohol polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1054860C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6632385B2 (en) * | 2001-03-23 | 2003-10-14 | First Quality Nonwovens, Inc. | Condrapable hydrophobic nonwoven web and method of making same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3441547A (en) * | 1966-12-30 | 1969-04-29 | Air Reduction | Vinyl acetate-methyl butenol copolymers |
| JPS62207304A (en) * | 1986-03-08 | 1987-09-11 | Denki Kagaku Kogyo Kk | Production of copolymer having surface activity |
-
1995
- 1995-06-05 CN CN95190597A patent/CN1054860C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3441547A (en) * | 1966-12-30 | 1969-04-29 | Air Reduction | Vinyl acetate-methyl butenol copolymers |
| JPS62207304A (en) * | 1986-03-08 | 1987-09-11 | Denki Kagaku Kogyo Kk | Production of copolymer having surface activity |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1154120A (en) | 1997-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1120184C (en) | Vinyl alcohol polymer and its composition | |
| JP6110678B2 (en) | Hydroxymethyl group-containing vinyl alcohol polymer | |
| CN1164676C (en) | Water soluble resin composition and water soluble film | |
| US5272200A (en) | Aqueous dispersion and substrate coated with the same | |
| JP4772175B2 (en) | Vinyl alcohol polymer and composition | |
| CN102731710B (en) | Carboxyl modified polyvinyl alcohol and method for preparing same | |
| CN106029713B (en) | Modified polyvinylalcohol and its manufacturing method | |
| JP2015034262A (en) | Modified vinyl alcohol-based polymer | |
| JP3618400B2 (en) | Vinyl alcohol polymer | |
| US5866655A (en) | Vinyl alcohol polymer | |
| JP4368595B2 (en) | Hot melt adhesive | |
| US5367015A (en) | Polyvinyl acetals having improved melt viscosity characteristics, processes for their preparation and their use | |
| JP3618440B2 (en) | Vinyl alcohol polymer | |
| CN1054860C (en) | Vinyl alcohol polymer | |
| JPH05239301A (en) | Extrudable polyvinyl alcohol composition containing polyethylene oxide | |
| JP4132467B2 (en) | Production method of vinyl alcohol polymer | |
| JP5667533B2 (en) | Acrylic thermoplastic resin composition | |
| FI120694B (en) | The vinyl alcohol polymer | |
| CA2168549C (en) | Vinyl alcohol polymer | |
| CN1305506A (en) | New protective colloids in latices with improved film formation at low temp | |
| JPH05155919A (en) | Ethylene-vinyl alcohol copolymer terminal-modified with ion and its aqueous dispersion | |
| JP5349175B2 (en) | Aqueous dispersion | |
| JPH0948824A (en) | Resin for melt molding | |
| JP2001164069A (en) | Vinyl alcohol polymer composition and molded article | |
| JPH05331332A (en) | Aqueous dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20000726 Termination date: 20130605 |