CN1331704A - Process for preparing water-soluble styrenelacrylic resins by continuous bulk polymerization - Google Patents
Process for preparing water-soluble styrenelacrylic resins by continuous bulk polymerization Download PDFInfo
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- CN1331704A CN1331704A CN99814773A CN99814773A CN1331704A CN 1331704 A CN1331704 A CN 1331704A CN 99814773 A CN99814773 A CN 99814773A CN 99814773 A CN99814773 A CN 99814773A CN 1331704 A CN1331704 A CN 1331704A
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- 238000012662 bulk polymerization Methods 0.000 title claims abstract description 20
- 239000011347 resin Substances 0.000 title abstract description 38
- 229920005989 resin Polymers 0.000 title abstract description 38
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 30
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 13
- KTADTTCBDAMZIR-UHFFFAOYSA-N 2-(2-hydroxypropoxy)propan-1-ol;hydrate Chemical compound O.CC(O)COC(C)CO KTADTTCBDAMZIR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 26
- 239000002253 acid Substances 0.000 abstract description 21
- -1 acryl Chemical group 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000011877 solvent mixture Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 239000000976 ink Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000007639 printing Methods 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 210000000689 upper leg Anatomy 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000007858 starting material Substances 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
- C08F212/00—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 aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to a bulk polymerization process for preparing water-soluble styrene/acrylic resins, in which styrene and acryl monomers are polymerized in a solvent mixture of dipropylene glycol methyl ether and water in a temperature-controllable reactor equipped externally with an oil jacket containing a cooling coil therein and the resulting polymers are deprived of volatile contents in a falling-strand type devolatilizer. The water-soluble styrene/acrylic resins take industrial advantages over conventional resins because the resins, if polymerized at lower temperatures, show lower molecular weights, narrower molecular weight distributions, higher acid values and lower volatile content.
Description
Technical field
The present invention relates to adopt continuous bulk polymerization to prepare the method for water-soluble phenylethene/acrylic resin.Or rather, the present invention relates to prepare the method for the low-molecular weight polymer of narrow molecular weight distributions, high acid value and low-content volatile composition by continuous bulk polymerization.
Technical background
Most printing ink, paint and the coating that uses all with an organic solvent at present.This is that the organic materials of organic solvent can evaporate because printing ink, paint and coating are when using, and finds that now they can cause serious topsoil.In addition, organic solvent is because the very possible initiation fire of its inflammableness.
As the alternative method of avoiding these problems, the highly filled liquid coating based on water-soluble phenylethene/acrylic resin has been proposed.In fact, these highly filled liquid coatings are good not causing aspect the topsoil.Opposite with organic solvent based coating, highly filled liquid coating also reduces the cost of required resource, energy and Working environment, and can not cause fire or blast.
But,, then must solve because the problem that the viscosity of highly filled caused printing ink, paint and coating increases in order to make high solid content liquid coating useful.Even the increase of the molecular weight of water-soluble phenylethene/acrylic resin little by little, and it is a lot of all can to cause printing ink, paint and dope viscosity to increase.As a result, high molecular weight resin just is subjected to increasing the restriction of solids content.For example, when using weight-average molecular weight to be about 50,000-100, when water-soluble phenylethene/acrylic resin of 000 prepared water color ink, paint or coating, the solids content of allowing was up to 50%.On the contrary, weight-average molecular weight be water-soluble phenylethene/acrylic resin of 5000-15000 can make printing ink, paint and coating solids content up to 70-80%, and can not cause problem.But in this case, because the effect of high molecular part in the resin, wide molecular weight distribution can increase the viscosity of printing ink, paint and coating.Therefore, just require narrow molecular weight distribution, to obtain highly filled water color ink or paint.
Water-soluble about styrene/acrylic resin, it by acidic-group, be generally carboxyl and provided.In order to introduce carboxyl in resin, acrylic or methacrylic acid is useful.Competent water-soluble in order to form, must have 200 or greater than 200 acid number.
When preparation printing ink or paint, the high-content volatile component in the water soluble resin is to form a large amount of foamy reasons.The workability of these foams meeting deterioration printing ink or paint.A large amount of foam killers can address this problem, but physicals is descended.Therefore, the volatile component that water soluble resin contains is few more, and workability is just good more.In addition, by using less foam killer can obtain better printing ink of physicals or paint.
Generally speaking, in order to prepare highly filled water color ink or paint, need that molecular-weight average is low, narrow molecular weight distribution, acid number height and the few water soluble resin of volatile component.
For example, use weight-average molecular weight 4000-16000, molecular weight distribution 2.2 or narrower, acid number 200 or water-soluble phenylethene/acrylic resin higher, volatile component content 5%, make high solid content liquid coating.Satisfying the water-soluble phenylethene/acrylic resin of these conditions can not be made by common known solution polymerization or letex polymerization.In fact, solution polymerization process can be used to prepare the styrene/acrylic resin that molecular weight is about 10000-100000, and letex polymerization can be used to prepare molecular weight up to 1,000,000 resin.
US Patent No 4,414,370 have disclosed the continuous bulk polymerization process of preparation water-soluble phenylethene/acrylic resin, the document is pointed out, monomer is feeding continuously in the following manner, be that their stop 2 minutes or more progress row polymerization in the reactor of continuously stirring under 235-310 ℃ of temperature of reaction, and the polymer transport of making like this to exhaust section to remove volatile component.The document points out that also number-average molecular weight is that 1000-6000, molecular weight distribution can be polymerized by the monomer component that contains following monomeric mixture less than water-soluble phenylethene/acrylic resin of 2.0: vinylbenzene and alpha-methyl styrene (weight ratio is 1: 2-2: 1) and vinylformic acid (styrene mixture and acrylic acid weight ratio are 60: 40-80: 20), adopting 1-10 part (weight) TC as solvent, is benchmark with the total monomer weight.For the temperature of reaction of controlling reactor, external jacket and internal cooling coil pipe are installed, heat-transfer oil is flowed in chuck and spiral coil cooling tube.
But, come control reaction temperature also to have problems by the combination of oil jacket that is contained in inside reactor and outside respectively and spiral coil cooling tube, promptly, be difficult to controlling reactor temperature inside equably because inside reactor and outside temperature head are bigger.The high reaction temperature of previous patent also is a factor that increases preparation cost.Demand is than the novel method that can prepare molecular weight and molecular weight distribution and above-mentioned approaching water-soluble phenylethene/acrylic resin under the low reaction temperatures.As the solvent TC of the viscosity of control reaction mixture can with vinylformic acid generation esterification, reduced the acid number of water soluble resin product.As a result, the water-soluble of resin descended.Therefore, demand does not have the solvent that influences and can control the viscosity of reaction to product as far as possible yet.
We know, above-mentioned patent is described to remove the volatile component that removes in the bulk polymerization of unreacted monomer and residual solvent from resin product, in the efficient of the whole technology of decision with control the product physicals and for example important effect is arranged aspect the volatile component content.All these do not see play-by-play as yet.
The content of invention
The inventor has carried out the extensive research that repeats to effective continuous bulk polymerization process, found that, spiral coil cooling tube/chuck that use is combined into one, temperature controllable reactor and strand type (falling-strand type) the devolatilization device that falls, at a lower temperature, Acrylic Acid Monomer and styrene monomer can be copolymerized into the low-molecular weight polymer that is applicable to paint, printing ink and coating in water-containing solvent.
Therefore, an object of the present invention is to provide the continuous bulk polymerization process of the water-soluble phenylethene/acrylic resin of preparation lower molecular weight, narrow molecular weight distributions, high acid value and low-content volatile composition.
This purpose is realized by such method, the mixed solvent of wherein about 5-15 part (weight) dipropylene glycol methyl ether and water (is benchmark with 100 parts of (weight) reaction monomers) adds the outside continuously and has in the temperature controllable reactor of the oil jacket that includes spiral coil cooling tube, monomer stops in reactor under 150-220 ℃ and carried out copolymerization in 10-20 minute, polymer transport under-500 to-750 mmhg vacuum at the whereabouts of 180-210 ℃ of operation thigh type exhaust section, from polymkeric substance, remove volatile component.
Brief description of drawings
Fig. 1 is the synoptic diagram of explanation continuous bulk polymerization process of the present invention.
The preferred forms of invention
The present invention relates to styrene monomer and Acrylic Acid Monomer (below be called " monomer ") carry out continuous bulk polymerization under the temperature of reaction lower than prior art method.For this mass polymerization, the mixture that uses dipropylene glycol methyl ether (DPM) and water is as solvent.The method according to this invention, the water-soluble phenylethene/acrylic resin of narrow molecular weight distributions can obtain under about 150-220 ℃ temperature of reaction.Can choose the adding a-Methylstyrene Low-Polymer wantonly, control the molecular weight and the molecular weight distribution of resin.
With reference to accompanying drawing, it has illustrated the operation of the continuous bulk polymerization that obtains water-soluble phenylethene/acrylic resin.As shown in the figure, method of the present invention is to use monomer container 1 and 2, the reactor 3 of two band stirrings, fall a strand type exhaust section 4, distillation column 5 and MONOMER RECOVERY container 6 to implement.
From being with the monomer container 1 or 2 that stirs to reactor 3, monomer feeds with constant speed.The liquid level of controlling reactor 3, purpose are to make the monomeric residence time that adds reactor 3 be about 10-20 minute.The capacity of reactor can for example be 75 liters.In order to control the temperature of reaction of continuous bulk polymerization effectively, on reactor, load onto heat-transfer oil mobile chuck therein.Also in chuck, load onto heat-transfer oil mobile spiral coil cooling tube therein.Utilize this temperature-control device that is combined into one, just the temperature of reaction in the controlling reactor easily.Adopt equipment as shown in the figure, utilize mass polymerization, just can to make weight-average molecular weight be 3000-10000, molecular weight distribution less than water-soluble phenylethene/acrylic resin of 2.0 by monomer.
During through reactor, monomer polymerization becomes water soluble resin, and then, this resin transfer therefrom removes volatile component to strand type exhaust section 4 that falls.Exhaust section by the heat-transfer oil of being equipped therein the mobile chuck keep steady temperature, and keep the constant vacuum states by means of vacuum pump 7.Through after the exhaust section 4, the volatile component content of polymer product becomes below 2%.
The material of the mixed solvent that contains unreacted monomer, high boiler material and dipropylene glycol and water of the volatile component that removes at exhaust section separates high boiler material through distillation column 5, then is stored in the MONOMER RECOVERY container 6, adds reactor at last again.
US Patent No 4,414 in 371, with the solvent of TC as mass polymerization, is used for the absorption reaction heat and the viscosity of control reactant.As mentioned above, as the result of the esterification between the carboxyl of the hydroxyl of vehicle substance and the resin made, this material chemistry is bonded in the molecule of water soluble resin.As a result, this material has just been lost the function of the solvent of himself, and this can make the viscosity of reaction mixture increase, and very difficult controlling reactor temperature.In addition, esterification has reduced the acid number of water soluble resin, makes its water-soluble decline.
In the present invention, dipropylene glycol methyl ether still together is used as solvent with water as solvent.The consumption of this mixed solvent (is benchmark with 100 parts of (weight) monomers) accounts for 5-15 part (weight).Except can advantageously controlling the viscosity of reaction mixture, the water of coexistence also can suppress dipropylene glycol methyl ether and acroleic acid esterification.As a result, just can be made into water-soluble phenylethene/acrylic resin that acid number is 200-230.This mixed solvent preferably contains the 20-45% that has an appointment (weight) water.For example, if water-content is lower than 20% (weight), between dipropylene glycol methyl ether and the vinylformic acid esterification widely will take place, reduce the acid number of final product.On the other hand, if water-content is higher than 45% (weight), water will evaporate in a large number, thereby just can not control the viscosity of reaction mixture effectively, presses in the reactor to increase a lot.
In order to obtain best result, the weight ratio of styrene monomer and Acrylic Acid Monomer is 60 in the monomer mixture: 40-80: 20.Styrene monomer only contains vinylbenzene or contains it and the composition of alpha-methyl styrene, and vinylbenzene is 50 with the ratio of alpha-methyl styrene: 50-90: 10.For Acrylic Acid Monomer, only use vinylformic acid or use itself and the composition that is not higher than the alkyl acrylate of 20% (weight).
Can choose wantonly a-Methylstyrene Low-Polymer as molecular weight regulator.Preferred 2-6 part of the add-on of a-Methylstyrene Low-Polymer (weight) is a benchmark with 100 parts of (weight) monomer mixtures.For example, if the consumption of a-Methylstyrene Low-Polymer is very few, formed resin just has high molecular, and molecular weight distribution is wide.On the other hand, too much a-Methylstyrene Low-Polymer can form molecular weight and cross resin low thereby the physicals difference.
It is reported, if use as the α-Jia Jibenyixidanti of molecular resin amount and molecular weight distribution conditioning agent is a large amount of in the present invention, can influence dispersion (surface phenomena in water soluble paint and printing technology and the latex of pigment in resin unfriendly, M.K.Sharma edits, Plenum press publishes, New York, 1995, the 139-151 pages or leaves).Use a small amount of a-Methylstyrene Low-Polymer can make the outstanding water-soluble phenylethene/acrylic resin of colo(u)rant dispersion, and do not have color and smell problem.For a-Methylstyrene Low-Polymer, recommend " Techlon M21 Extra " available from Tekchem Corporation.
Because mass polymerization of the present invention is carried out at low temperatures, for example the t-butyl peroxy benzoic ether is better for low temperature initiators.Preferably about 3-6 part of its consumption (weight) is a benchmark with the monomer mixture gross weight.
The whereabouts thigh type exhaust section that is used in the present invention removing volatile component from product is than US Patent No 4,414, and the stirred vessel type exhaust section that uses in 370 is favourable, and advantage is that resin surface is long-pending and increases, makes to be easy to remove volatile component from resin.
Strand type exhaust section that falls preferably remains on 180-210 ℃.For example, temperature is lower than 180 ℃ in the exhaust section, and removing volatile component from resin will be the problem of difficulty.On the other hand, if strand type exhaust section that falls is heated above 210 ℃, the physicals of the resin of Xing Chenging just descends so.
When mass polymerization took place, exhaust section preferably moved under the vacuum of-750 to-500 mmhg.For example, be lower than under the vacuum of-750 mmhg, the flowable of resin can sharply reduce, and makes resin be difficult to carry.On the other hand, vacuum is higher than-500 mmhg, just is difficult to the volatile component in the abundant deresinate.
According to following illustrative embodiment, the present invention may be better understood, these embodiment is not interpreted as restriction the present invention.
Example I-V
In having the continuously stirring temperature controllable reactor of the oil jacket that includes spiral coil cooling tube, the outside adds styrene monomer (vinylbenzene and alpha-methyl styrene) and Acrylic Acid Monomer (vinylformic acid), and as shown in table 1 below, preparation water-soluble phenylethene/acrylic resin.
Be aggregated in the t-butyl peroxy benzoic ether and have initiation down.The consumption of this polymerization starter is 3.5 parts (weight), is benchmark with the gross weight of monomer mixture.For this polymerization, using 15 parts of (weight) water-contents is the dipropylene glycol methyl ether of 35% (weight) and the mixed solvent of water, is benchmark with 100 parts of (weight) monomer mixtures.Under 150-220 ℃ condition of different temperatures, carry out polymerization.The resin that aggregates into therefrom removes volatile component through strand type exhaust section that falls.Simultaneously, exhaust section is in-750 mmhg, 195 ℃ of operations down.
Table 1
| The embodiment numbering | I | ????II | ?III | ????IV | ?V |
| Vinylbenzene (part (weight)) | 35 | ????35 | ?35 | ????35 | ?35 |
| Alpha-methyl styrene (part (weight)) | 32 | ????32 | ?32 | ????32 | ?32 |
| Vinylformic acid (part (weight)) | 33 | ????33 | ?33 | ????33 | ?33 |
| Temperature of reaction (℃) | 150 | ????180 | ?200 | ????210 | ?220 |
| Number-average molecular weight, Mw, Mn | 5000 | ????4800 | ?4400 | ????3600 | ?3100 |
| Weight-average molecular weight, Mw, Mw | 9800 | ????8700 | ?7500 | ????6200 | ?5200 |
| Molecular weight distribution, Mw | 1.9 | ????1.8 | ?1.7 | ????1.7 | ?1.7 |
| Acid number | 223 | ????223 | ?225 | ????225 | ?226 |
| Volatile component content (%) | 1.5 | ????1.5 | ?1.3 | ????1.2 | ?1.2 |
Comparative Examples I-III
These embodiment have compared the temperature control ability between reactor of the present invention and the popular response device.
Prepared water-soluble phenylethene/acrylic resin respectively in the mode similar to example II, IV and V, difference is that heat-transfer oil is flow through is arranged on the spiral coil cooling tube of oil jacket inside, and makes it to flow through the spiral coil cooling tube that temporarily is arranged on inside reactor.The physicals of the resin of making is as shown in table 2 below.
Table 2
| The Comparative Examples numbering | ????C.I | ????C.II | ????C.III |
| Temperature of reaction (℃) | ????180 | ????210 | ????220 |
| Number-average molecular weight, Mw, Mn | ????4500 | ????3250 | ????2750 |
| Weight-average molecular weight, Mw, Mw | ????10550 | ????7850 | ????6700 |
| Molecular weight distribution, Mw | ????2.34 | ????2.41 | ????2.43 |
| Acid number | ????220 | ????222 | ????222 |
| Volatile component content (%) | ????1.5 | ????1.4 | ????1.4 |
From table 1 and 2 as seen, the molecular weight distribution of the water-soluble phenylethene/acrylic resin that under same temperature, obtains with the popular response device, wideer than the water-soluble phenylethene/acrylic resin that obtains with reactor of the present invention.This is because even under same average reaction temperature, the temperature deviation difference of reactor makes local temperature variant.Therefore, the popular response device with external belt oil jacket, inner band spiral coil cooling tube is difficult to controlled temperature.
Example VI-IX
For the influence to the resin physicals of the operational condition of studying exhaust section, polymerization is in the mode identical with EXAMPLE IV, but carries out under the temperature and pressure condition of exhaust section as shown in table 3 below.The result is as shown in table 3.
Table 3
| The embodiment numbering | ?IV | ?VI | ?VII | ?VIII | ?IX |
| The exhaust section temperature (℃) | ?195 | ?210 | ?180 | ?210 | ?180 |
| Exhaust section pressure (mmhg) | ?-750 | ?-750 | ?-750 | ?-500 | ?-600 |
| Number-average molecular weight, Mw, Mn | ?3600 | ?3600 | ?3600 | ?3600 | ?3600 |
| Weight-average molecular weight, Mw, Mw | ?6200 | ?6200 | ?6200 | ?6200 | ?6200 |
| Molecular weight distribution, Mw | ?1.7 | ?1.7 | ?1.7 | ?1.7 | ?1.7 |
| Acid number | ?225 | ?225 | ?226 | ?225 | ?224 |
| Volatile component content (%) | ?1.2 | ?1.1 | ?1.5 | ?1.7 | ?1.8 |
Comparative Examples I V and V
For relatively,, but under exhaust section condition as shown in table 4 below, prepare water-soluble phenylethene/acrylic resin in the mode identical with EXAMPLE IV.The result is as shown in table 4.
Table 4
| The embodiment numbering | ?IV | ?C.IV | ?C.V |
| The exhaust section temperature (℃) | ?195 | ?170 | ?235 |
| Exhaust section pressure (mmhg) | ?-750 | ?-350 | ?-750 |
| Number-average molecular weight, Mw, Mn | ?3600 | ?3600 | ?2800 |
| Weight-average molecular weight, Mw, Mw | ?6200 | ?6200 | ?5850 |
| Molecular weight distribution, Mw | ?1.7 | ?1.7 | ?2.1 |
| Acid number | ?225 | ?225 | ?214 |
| Volatile component content (%) | ?1.2 | ?3.8 | ?0.6 |
Table 4 data declaration, when exhaust section keeps low temperature and high pressure, volatile component content height, and the exhaust section condition of high temperature and low pressure can reduce volatile component content, but can make molecular weight distribution wide, and acid number is reduced to a certain degree.
Embodiment X-XIII
Prepare water-soluble phenylethene/acrylic resin in the mode similar to EXAMPLE IV, difference is to change the consumption and the water-content of the mixed solvent of dipropylene glycol methyl ether and water, and is as shown in table 5 below.
Comparative Examples VI
Repeat the step identical with embodiment X, difference is that dipropylene glycol methyl ether is used alone as solvent.
The result is as shown in table 5 below.
Table 5
* independent dipropylene glycol methyl ether
| The embodiment numbering | ?IV | ?X | ?XI | ?XII | ?XIII | ?C.VI |
| Solvent load (part (weight)) | ?15 | ?10 | ?15 | ?5 | ?10 | ?15* |
| Water-content in the solvent (% (weight)) | ?35 | ?35 | ?45 | ?20 | ?25 | ?0 |
| Number-average molecular weight Mw, Mn | ?3600 | ?3500 | ?3600 | ?3200 | ?3600 | ?3100 |
| Weight-average molecular weight, Mw, Mw | ?6200 | ?6300 | ?6200 | ?6500 | ?6200 | ?6500 |
| Molecular weight distribution, Mw | ?1.7 | ?1.8 | ?1.7 | ?1.8 | ?1.8 | ?2.1 |
| Acid number | ?225 | ?220 | ?230 | ?205 | ?203 | ?180 |
| Volatile component content (%) | ?1.2 | ?1.1 | ?1.3 | ?1.1 | ?1.2 | ?1.5 |
Embodiment XIV-XVII
In order to study the influence of styrene monomer content to the resin physicals, polymerization is still carried out under the condition of change styrene monomer content as shown in table 6 below in the mode identical with EXAMPLE IV.The result is as shown in table 6.
Table 6
| The embodiment numbering | ?IV | ????XIV | ????XV | ????XIV | ????XVII |
| Vinylbenzene (part (weight)) | ?35 | ????43 | ????52 | ????60 | ????67 |
| Alpha-methyl styrene (part (weight)) | ?32 | ????24 | ????15 | ????7 | ????0 |
| Vinylformic acid (part (weight)) | ?33 | ????33 | ????33 | ????33 | ????33 |
| Number-average molecular weight, Mw, Mn | ?3600 | ????3200 | ????3750 | ????3800 | ????4100 |
| Weight-average molecular weight, Mw, Mw | ?6200 | ????5750 | ????6800 | ????7500 | ????8150 |
| Molecular weight distribution, Mw | ?1.7 | ????1.8 | ????1.8 | ????2.0 | ????2.0 |
| Acid number | ?225 | ????223 | ????225 | ????227 | ????227 |
| Volatile component content (%) | ?1.2 | ????1.4 | ????1.3 | ????1.3 | ????1.3 |
Embodiment XVIII-XX
In order to study the influence of Acrylic Acid Monomer content to the resin physicals, polymerization is still carried out under the condition of change Acrylic Acid Monomer content as shown in table 7 below in the mode identical with EXAMPLE IV.The result is as shown in table 7.
Table 7
| The embodiment numbering | ?IV | ???XVIII | ???XIX | ????XX |
| Vinylbenzene (part (weight)) | ?35 | ????35 | ????35 | ????35 |
| Alpha-methyl styrene (part (weight)) | ?32 | ????32 | ????32 | ????32 |
| Vinylformic acid (part (weight)) | ?33 | ????29.5 | ????28.5 | ????27 |
| Methyl acrylate (part (weight)) | ?0 | ????3.5 | ????4.5 | ????6 |
| Number-average molecular weight, Mw, Mn | ?3600 | ????3650 | ????3700 | ????3700 |
| Weight-average molecular weight, Mw, Mw | ?6200 | ????6600 | ????6700 | ????7350 |
| Molecular weight distribution, Mw | ?1.7 | ????1.8 | ????1.8 | ????2.0 |
| Acid number | ?225 | ????220 | ????213 | ????204 |
| Volatile component content (%) | ?1.2 | ????1.3 | ????1.4 | ????1.4 |
Comparative Examples VII
According to US Patent No 4,414,370 methods that propose, employing has heat-transfer oil mobile external jacket and the inner continuously stirring temperature controllable reactor that is provided with spiral coil cooling tube therein, by consumption and the temperature of reaction shown in styrene monomer (vinylbenzene and alpha-methyl styrene) and Acrylic Acid Monomer (vinylformic acid) following table 8, preparation water-soluble phenylethene/acrylic resin.For this polyreaction, TC is as reaction solvent.The result is as shown in table 8.
Table 8
| The embodiment numbering | ???C.VII |
| Vinylbenzene (part (weight)) | ????31 |
| Alpha-methyl styrene (part (weight)) | ????37 |
| Vinylformic acid (part (weight)) | ????32 |
| Temperature of reaction (℃) | ????263 |
| Solvent load (part (weight)) | ????20 |
| The exhaust section temperature (℃) | ????263 |
| Number-average molecular weight, Mw, Mn | ????1700 |
| Weight-average molecular weight, Mw, Mw | ????2650 |
| Molecular weight distribution, Mw | ????1.56 |
| Acid number | ????160 |
Embodiment XXI and XXII
In order to study the influence of a-Methylstyrene Low-Polymer to the resin physicals, polymerization is still carried out under the condition of change a-Methylstyrene Low-Polymer content as shown in table 9 below in the mode identical with EXAMPLE IV.The result is as shown in table 9.
Table 9
| The embodiment numbering | ???XXI | ???XXII |
| Vinylbenzene (part (weight)) | ????35 | ????35 |
| Alpha-methyl styrene (part (weight)) | ????32 | ????32 |
| Vinylformic acid (part (weight)) | ????33 | ????33 |
| A-Methylstyrene Low-Polymer (part (weight)) | ????3 | ????5 |
| Number-average molecular weight, Mw, Mn | ????3800 | ????3950 |
| Weight-average molecular weight, Mw, Mw | ????6100 | ????5900 |
| Molecular weight distribution, Mw | ????1.6 | ????1.5 |
| Acid number | ????226 | ????225 |
| Volatile component content (%) | ????1.2 | ????1.2 |
Practicality
As mentioned above, continuous bulk polymerization process of the present invention is having a great difference with ordinary method aspect solvent (mixture of dipropylene glycol methyl ether and water), temperature of reaction control mode, exhaust section type and the exhaust section operational condition used.Water-soluble phenylethene/acrylic resin prepared according to the methods of the invention has the advantage of the industrial utilization better than conventional resin, because resin of the present invention is if the molecular weight of the resin that polymerization at a lower temperature will make than ordinary method is low, narrow molecular weight distribution, acid number height and volatile component content are low.
Described the present invention with illustrative approach above, understand that employed technical terms is illustrative, rather than restrictive.According to the above description, can carry out multiple improvement and variation to the present invention.Therefore, understand within the scope of the appended claims, also can implement the present invention in the mode different with above-mentioned concrete mode.
Claims (9)
1. method for preparing water-soluble phenylethene/acrylic resin by continuous bulk polymerization, wherein styrene monomer component and Acrylic Acid Monomer component polymerization in the mixed solvent of dipropylene glycol methyl ether and water under 150-220 ℃ of temperature of reaction, form polymkeric substance, this polymkeric substance removes volatile component by share split falling type exhaust section.
2. the method for claim 1, the consumption of wherein said mixed solvent is about 5-15 part (weight), is benchmark with 100 parts of (weight) monomer components.
3. the method for claim 1, the water-content of wherein said mixed solvent is about 20-45% (weight).
4. the method for claim 1, the weight ratio of wherein said styrene monomer component and Acrylic Acid Monomer component is 60: 40-80: 20.
5. as claim 1 or 4 described methods, wherein said styrene monomer component only comprises vinylbenzene or comprises vinylbenzene and the composition of alpha-methyl styrene, and the weight ratio of vinylbenzene and alpha-methyl styrene is 50: 50-90: 10.
6. as claim 1 or 4 described methods, wherein said Acrylic Acid Monomer component only comprises vinylformic acid or comprises vinylformic acid and the composition of the alkyl acrylate of no more than 20% (weight).
7. the method for claim 1, wherein said exhaust section moves under the vacuum pressure of 180-210 ℃ temperature ,-500 to-750 mmhg.
8. the method for claim 1, wherein said monomer component externally are equipped with polymerization in the continuously stirring temperature controllable reactor of the oil jacket that includes spiral coil cooling tube.
9. the method for claim 1, wherein said monomer component also contains 2-6 part (weight) a-Methylstyrene Low-Polymer of having an appointment, and is benchmark with 100 parts of (weight) monomer components.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019980056434A KR100301126B1 (en) | 1998-12-19 | 1998-12-19 | Method for producing styrene / acrylic water-soluble resin by continuous bulk polymerization |
| KR1998/056434 | 1998-12-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1331704A true CN1331704A (en) | 2002-01-16 |
| CN1146579C CN1146579C (en) | 2004-04-21 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998147737A Expired - Lifetime CN1146579C (en) | 1998-12-19 | 1999-03-04 | Process for preparing water-soluble styrenelacrylic resins by continuous bulk polymerization |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP3570624B2 (en) |
| KR (1) | KR100301126B1 (en) |
| CN (1) | CN1146579C (en) |
| HK (1) | HK1043800B (en) |
| ID (1) | ID29615A (en) |
| WO (1) | WO2000037506A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100560622C (en) * | 2008-02-27 | 2009-11-18 | 广东天龙油墨集团股份有限公司 | The continuous processing mass polymerization prepares the water miscible acrylic resin of polymolecularity and preparation method and the application in printing ink thereof |
| CN103097470A (en) * | 2010-08-05 | 2013-05-08 | 韩华石油化学株式会社 | High-efficiency heat-dissipating paint composition using a carbon material |
| CN113384489A (en) * | 2021-06-16 | 2021-09-14 | 宇虹颜料股份有限公司 | Processing method of water-based nail polish preparation |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2928227B1 (en) * | 2008-02-29 | 2010-04-02 | Commissariat Energie Atomique | PROCESS FOR MANUFACTURING ION CONDUCTION POLYMERIC MEMBRANE FOR FUEL CELL. |
| KR101495211B1 (en) | 2013-01-08 | 2015-02-24 | 한화케미칼 주식회사 | Resin for blister package and preparation method thereof |
| KR102687446B1 (en) * | 2020-08-31 | 2024-07-23 | 한화솔루션 주식회사 | Method for preparing styrene maleic anhydride resin through continuous polymerization and styrene maleic anhydride resin preprared thereby |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4451612A (en) * | 1980-09-22 | 1984-05-29 | Mobil Oil Corporation | Continuous process for the preparation of rubber modified polymers |
| US4414370A (en) * | 1981-01-09 | 1983-11-08 | S. C. Johnson & Son, Inc. | Process for continuous bulk copolymerization of vinyl monomers |
| WO1982002387A1 (en) * | 1981-01-09 | 1982-07-22 | & Son Inc S C Johnson | Process for continuous bulk copolymerization of vinyl monomers and product thereof |
| JPS6058773B2 (en) * | 1981-06-30 | 1985-12-21 | 日立金属株式会社 | Ni-Cr-W alloy with improved high temperature fatigue strength and its manufacturing method |
| DE68903655T2 (en) * | 1988-03-17 | 1993-04-08 | Dainippon Ink & Chemicals | METHOD FOR PRODUCING A STYRENE / METHACRYLIC ACID COPOLYMER. |
| DE19524181A1 (en) * | 1995-07-03 | 1997-01-09 | Basf Ag | Process and device for the continuous production of polymers |
-
1998
- 1998-12-19 KR KR1019980056434A patent/KR100301126B1/en not_active IP Right Cessation
-
1999
- 1999-03-04 ID IDW00200101329A patent/ID29615A/en unknown
- 1999-03-04 WO PCT/KR1999/000103 patent/WO2000037506A1/en active Search and Examination
- 1999-03-04 JP JP2000589575A patent/JP3570624B2/en not_active Expired - Lifetime
- 1999-03-04 CN CNB998147737A patent/CN1146579C/en not_active Expired - Lifetime
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2002
- 2002-07-16 HK HK02105247.8A patent/HK1043800B/en not_active IP Right Cessation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100560622C (en) * | 2008-02-27 | 2009-11-18 | 广东天龙油墨集团股份有限公司 | The continuous processing mass polymerization prepares the water miscible acrylic resin of polymolecularity and preparation method and the application in printing ink thereof |
| CN103097470A (en) * | 2010-08-05 | 2013-05-08 | 韩华石油化学株式会社 | High-efficiency heat-dissipating paint composition using a carbon material |
| CN103097470B (en) * | 2010-08-05 | 2015-10-14 | 韩华石油化学株式会社 | Utilize the high efficiency heat radiation coating composition of carbon material |
| US9624379B2 (en) | 2010-08-05 | 2017-04-18 | Hanwha Chemical Corporation | High-efficiency heat-dissipating paint composition using a carbon material |
| CN113384489A (en) * | 2021-06-16 | 2021-09-14 | 宇虹颜料股份有限公司 | Processing method of water-based nail polish preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000037506A1 (en) | 2000-06-29 |
| HK1043800B (en) | 2005-02-18 |
| KR100301126B1 (en) | 2001-09-06 |
| CN1146579C (en) | 2004-04-21 |
| ID29615A (en) | 2001-09-06 |
| KR20000040715A (en) | 2000-07-05 |
| HK1043800A1 (en) | 2002-09-27 |
| JP3570624B2 (en) | 2004-09-29 |
| JP2002533480A (en) | 2002-10-08 |
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