CN116023556B - Oil-soluble PVC (polyvinyl chloride) polymerization emulsion dispersion aid, preparation method and application - Google Patents
Oil-soluble PVC (polyvinyl chloride) polymerization emulsion dispersion aid, preparation method and application Download PDFInfo
- Publication number
- CN116023556B CN116023556B CN202111239921.XA CN202111239921A CN116023556B CN 116023556 B CN116023556 B CN 116023556B CN 202111239921 A CN202111239921 A CN 202111239921A CN 116023556 B CN116023556 B CN 116023556B
- Authority
- CN
- China
- Prior art keywords
- parts
- oil
- pvc
- polymerization
- soluble
- 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.)
- Active
Links
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 92
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 92
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 54
- 239000000839 emulsion Substances 0.000 title claims abstract description 50
- 239000006185 dispersion Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 229920001214 Polysorbate 60 Polymers 0.000 claims abstract description 11
- 239000004147 Sorbitan trioleate Substances 0.000 claims abstract description 11
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims abstract description 11
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 11
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 11
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 11
- 235000019337 sorbitan trioleate Nutrition 0.000 claims abstract description 11
- 229960000391 sorbitan trioleate Drugs 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims abstract description 9
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 5
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 4
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940035893 uracil Drugs 0.000 claims description 3
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 239000004368 Modified starch Substances 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 235000013336 milk Nutrition 0.000 claims 1
- 239000008267 milk Substances 0.000 claims 1
- 210000004080 milk Anatomy 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 39
- 229920005989 resin Polymers 0.000 abstract description 39
- 239000002245 particle Substances 0.000 abstract description 33
- 238000009826 distribution Methods 0.000 abstract description 6
- 238000004040 coloring Methods 0.000 abstract description 5
- 239000011164 primary particle Substances 0.000 abstract description 5
- 239000003995 emulsifying agent Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000004581 coalescence Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012760 heat stabilizer Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
An oil-soluble PVC polymerization emulsion dispersion auxiliary agent, a preparation method and application thereof belong to the technical field of polyvinyl chloride polymerization auxiliary agents. At present, a serious problem with PVC resins is the transmission Huang Faan of transparent products. The invention comprises deionized water in parts by weight: 300-350 parts of a lubricant; 3- (dimethylamino) propyl acrylate: 2.8-3.2 parts; polyoxyethylene sorbitan trioleate: 8.8-9.2 parts; pentaethylene glycol: 1.4-1.6 parts; tetraethylene glycol: 2.4-2.6 parts; hydrotalcite: 25-35; stabilizing agent: 23-28 parts of a lubricant; an antioxidant: 40-50 parts of a lubricant. Four compounded hydrophobic and lipophilic emulsifying agents are adopted as carriers, a small amount of stabilizing agents, antioxidants and transparent hydrotalcite MAGECELER-1 are introduced into a polymerization dispersion system, and dispersed in a primary particle matrix along with polymerization reaction in the PVC polymerization process, so that the color change of PVC resin is inhibited on the premise of not influencing the growth and coalescence of primary particles, the particle size distribution of resin particles is narrowed, and the coloring performance and the processing performance of PVC products are improved.
Description
Technical Field
An oil-soluble PVC polymerization emulsion dispersion auxiliary agent, a preparation method and application thereof belong to the technical field of polyvinyl chloride polymerization auxiliary agents.
Background
PVC resin is widely applied to the fields of manufacturing pipes, pipe fittings, sheets, films, disposable medical appliances and the like, and can be further chlorinated to prepare chlorinated polyvinyl chloride resin. At present, a serious problem with PVC resins is the transmission Huang Faan of transparent products.
The cause of yellowing and darkening of the PVC transparent product is mainly the poor thermal stability of the resin, and the main cause of poor thermal stability is the unstable structure such as double bonds in PVC molecules, allyl chloride and the like, and the insufficient thermal stability of the PVC terminator.
In the prior art, the yellowing and darkening problems of PVC transparent products are not solved, and various means such as a composite terminator, a whitening agent or a heat stabilizer are generally adopted so as to obtain higher ageing whiteness or prolong the heat stability time and improve the heat stability. However, the basic principle of the scheme is that the method is added when the polymerization pressure drop reaches a specific value and the conversion rate of the polymerized VCM monomer reaches 80-80% in the later stage of the polymerization reaction. In the later stage of PVC polymerization reaction, primary PVC particles or sub-particles formed by aggregation are formed, most of the PVC heat stabilizer added with the terminator is adsorbed on the particle surfaces of PVC resin or the outer surfaces of gaps in the resin after the PVC heat stabilizer is added, and the heat stabilizer is not in disperse contact with PVC molecules to achieve molecular level. Therefore, heat stabilizers generally exert a heat stabilizing effect in the form of a surface, which also results in yellowing and darkening of PVC molecules which are unavoidable in long-term use.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the dispersing auxiliary agent is suitable for PVC polymerization, especially oil-soluble PVC polymerization, effectively inhibits decomposition and discoloration during PVC resin processing, improves initial coloring performance of PVC resin, effectively reduces usage amount of heat stabilizer, narrows resin particle distribution, and shortens plasticizer absorption time.
The technical scheme adopted for solving the technical problems is as follows: the oil-soluble PVC polymerization emulsion dispersion auxiliary agent is characterized in that: comprises the following components in parts by weight: deionized water: 300-350 parts of a lubricant; 3- (dimethylamino) propyl acrylate: 2.8-3.2 parts; polyoxyethylene sorbitan trioleate (Tween 85): 8.8-9.2 parts; pentaethylene glycol: 1.4-1.6 parts; tetraethylene glycol: 2.4-2.6 parts; hydrotalcite (MAGECELER-1): 25-35; stabilizing agent: 23-28 parts of a lubricant; an antioxidant: 40-50 parts of a lubricant.
According to the invention, the two nonionic surfactants of 3- (dimethylamino) propyl acrylate and polyoxyethylene sorbitan trioleate Tween85 are compounded with the dosage proportion of the pentaglycol and the tetraethylene glycol, so that a stable density gradient between water and the heat stabilizer, the antioxidant and the compound surfactant is established, and the phenomenon of demulsification and layering in the storage and use of the dispersant emulsion is avoided. The polarity complementation of the 3- (dimethylamino) propyl acrylate and the polyoxyethylene sorbitan trioleate Tween85 compound surfactants can enhance the interfacial strength between the stabilizer, hydrotalcite and antioxidant particles and water, effectively avoid collision agglomeration among the compound heat stabilizer particles under the condition of strong mechanical stirring, solve the problem of poor mechanical stirring resistance of emulsion, and obtain the compound dispersant emulsion with good particle size stability under the condition of strong mechanical stirring. And the HLB value of the composite surfactant is matched with the uniform dispersion of the auxiliary agent system, so that the dispersion effect of the surfactant in the dispersion auxiliary agent is better.
Four compounded hydrophobic and lipophilic emulsifying agents are adopted as carriers, a small amount of stabilizing agents, antioxidants and transparent hydrotalcite MAGECELER-1 are introduced into a polymerization dispersion system, the stabilizing agents, antioxidants and transparent hydrotalcite MAGECELER-1 are dispersed in a primary particle matrix along with polymerization reaction in the PVC polymerization process, the polymerization reaction maintains proper particle adhesion rate on the macro-scale on the premise of not influencing the growth and aggregation of primary particles, the aggregation of the primary particles is reduced on the micro-scale, the porosity is improved, the uniformity of macro-particles is improved, the initial coloring performance of PVC resin processing is improved, the PVC resin is endowed with more excellent optical performance, the oil-soluble emulsion dispersion auxiliary agent is added into the polymerization system along with a dispersing agent in the PVC polymerization reaction, the particle size of the polymerized PVC resin is moderate, the particle size distribution is narrowed, the whiteness (160 ℃ for 10 min) of the resin is improved, the plasticizer absorption time is shortened, and three optical performance indexes of transparent sheets prepared from the PVC resin are obviously improved.
Preferably, the stabilizer is lanthanum acetylacetonate and uracil in a weight ratio of 1.5-2.5: 1, and mixing.
The preferred stabilizers are more suitable for oil-soluble PVC polymerization processes, improve the thermal stability of the final PVC article, and do not have a polymerization inhibiting effect on the reaction process.
Preferably, the antioxidant is antioxidant 1076 and antioxidant DLTDP according to the weight ratio of 0.8-1.5: 1, and mixing.
The optimized antioxidant can ensure that the final PVC product has the optimal antioxidant effect, and further avoids Huang Faan.
Preferably, the composition comprises the following components in parts by weight: deionized water: 320 parts; 3- (dimethylamino) propyl acrylate: 3 parts; polyoxyethylene sorbitan trioleate: 9 parts; pentaethylene glycol: 1.5 parts; tetraethylene glycol: 2.5 parts; hydrotalcite: 30; stabilizing agent: 25 parts; an antioxidant: 45 parts.
The preferable weight ratio has the optimal dispersion assisting, stabilizing and oxidation resistance, the PVC resin particles are distributed more narrowly, the uniformity is higher, and the specific surface area of the resin is higher.
A preparation method of an oil-soluble PVC (polyvinyl chloride) polymerization emulsion dispersion aid is characterized by comprising the following steps of: and adding the raw materials into an emulsifying container according to the weight part ratio, heating and dissolving, and shearing and emulsifying for 50-70 min to obtain the modified starch.
The index of the dispersion aid of the oil-soluble PVC polymerization emulsion prepared by the method is close to the average particle size (mum) of emulsion particles: the HLB value is 0.1-0.2, and the HLB value is 2.4-3.5, the shelf life of the polymer can reach 18 months, and the polymer is more suitable for dispersing antioxidants, stabilizers and dispersants in a polymerization system.
Further preferably, the heating and dissolving is heating to 45-50 ℃ and uniformly stirring.
Further preferably, the shear is emulsified to high shear at 5500 r/min.
The preferable stirring and shearing conditions can obtain the oil-soluble PVC polymerization emulsion dispersing auxiliary with more stable indexes, the dispersing auxiliary is stable and has longer storage life, even if layering or precipitation phenomenon occurs in the storage of the oil-soluble PVC polymerization emulsion dispersing auxiliary, the performance of the oil-soluble PVC polymerization emulsion dispersing auxiliary is not changed after uniform stirring.
The application of the oil-soluble PVC polymerization emulsion dispersion auxiliary agent is characterized in that: the dispersion is applied to ternary dispersion systems with PVA80, hydroxypropyl methyl cellulose E50 and PVA45 serving as dispersing agents.
In the ternary dispersion system, PVA80 with high gel retention capacity and HPMC E50 with high dispersion capacity are used as main dispersants, excellent dispersion effect is provided, and the oil-soluble auxiliary dispersant PVA45 is easier to be matched with the oil-soluble PVC polymerization emulsion dispersion auxiliary agent to play a role of reaming the inside of resin particles, namely, the polarity difference of PVA45 components and other components in the ternary dispersion system is fully utilized, so that the dispersants and the dispersion auxiliary agent are mutually matched, the full dispersion of the antioxidant and the stabilizer in the polymerization process is realized, the dispersion effect of the dispersant is improved, and the effects of the antioxidant and the stabilizer are further improved.
It is further preferred that the oil-soluble PVC polymeric emulsion dispersion aid described above is added to the polymerization system after mixing with the dispersant prior to polymerization.
And the dispersing agent is mixed with the dispersing agent in advance, so that the uniform mixing of the dispersing auxiliary agent, the antioxidant, the stabilizer and the dispersing agent is ensured, the attaching effect is ensured, and the dispersing agent is fully participated in and dispersed in the subsequent polymerization reaction process.
Further preferably, the consumption of the oil-soluble PVC polymerization emulsion dispersing auxiliary is 180-220 ppm relative to the mass content of the VCM monomer.
The preferable dosage of the oil-soluble PVC polymerization emulsion dispersing auxiliary can ensure that the polyethylene product has good heat stability, oxidation resistance stability and other performances, and has the lowest influence on the polymerization process.
Compared with the prior art, the invention has the following beneficial effects: the dispersing auxiliary and the dispersing agent are added into a polymerization reaction system together, so that the dispersing effect of the heat stabilizer can be remarkably improved, the decomposition and discoloration of the PVC resin during the process of stripping, drying and mixing can be effectively inhibited, and the initial coloring performance of the PVC resin can be improved. The oil-soluble solvent can reduce small particles with the size of 5-25 mu m in the PVC resin, the large particles with the size of 150 mu m are also reduced, the particle size distribution of the particles is narrowed, the uniformity of the resin particles is better, and the dry flow time of the resin is shortened. The oil-soluble solvent in the dispersing agent increases the internal void ratio of the resin, increases the specific surface area of the internal void of the resin, increases the plasticizer absorption amount of the resin, shortens the plasticizer absorption time, and reduces the odor grade of the resin from 4.0 grade to 2.5-3.0 grade at a high temperature of 90 ℃.
Detailed Description
The present invention will be further described with reference to examples, examples 1 and 4 being preferred embodiments of the present invention.
The hydrotalcites used in the examples and comparative examples below had MgO/Al 2O3 =3.5, an average particle size of about 20nm and a specific surface area of 16m 2 /g.
Examples 1 to 3 and comparative examples 1 to 4
The proportions of the components in the examples and comparative examples of the oil-soluble PVC polymeric emulsion dispersing aid are shown in the following Table 1.
The preparation method of the oil-soluble PVC polymerization emulsion dispersing auxiliary comprises the steps of weighing deionized water, 3- (dimethylamino) propyl acrylate, polyoxyethylene sorbitan trioleate Tween85, pentaglycol, tetraethylene glycol, lanthanum acetylacetonate, an antioxidant 1076, an antioxidant DLTDP, hydrotalcite MAGECELER-1 and uracil according to a formula of a table 1, heating to 45-50 ℃ in an emulsifying container, stirring uniformly after all components are dissolved, and shearing an emulsifying machine at a high speed of 5500r/min for 60min in FA25D (FLUKO company product) high-speed shearing to obtain the oil-soluble PVC polymerization emulsion dispersing auxiliary.
Table 1 oil-soluble PVC polymeric emulsion dispersion aid formulation
。
The oil-soluble PVC polymerization emulsion dispersion auxiliary agent is detected, and the indexes are as follows: the average particle diameter of the emulsion particles is 0.1-0.2 mu m, and the HLB value is 2.4-3.5.
As can be seen from comparative examples 1 to 3 in table 1, when the emulsifier ratio lacks penta-or tetraglycol, the stable density gradient between surfactants is broken, the stable density gradient between the formulated dispersion auxiliary surfactants is broken, and further the reservoir is greatly shortened; from comparative examples 4 to 5 in Table 1, it can be seen that when either of the two nonionic surfactants, propyl 3- (dimethylamino) acrylate and polyoxyethylene sorbitan trioleate Tween85, is absent, a homogeneous PVC dispersion emulsion cannot be formed.
The invention can be explained that the stable density gradient between water, a heat stabilizer, an antioxidant and a compound surfactant is established by the use of the compound proportion of the two nonionic surfactants of 3- (dimethylamino) propyl acrylate and polyoxyethylene sorbitan trioleate Tween85, the pentaglycol and the tetraglycol, and the demulsification and layering of the dispersant emulsion in the storage and use process are avoided. The method is characterized in that the polarity complementation of the two composite surfactants of 3- (dimethylamino) propyl acrylate and polyoxyethylene sorbitan trioleate Tween85 can enhance the interfacial strength between lanthanum acetylacetonate, hydrotalcite and antioxidant particles and water, effectively avoid collision agglomeration among the composite heat stabilizer particles under the condition of strong mechanical stirring, solve the problem of poor mechanical stirring resistance of emulsion, obtain the composite dispersant emulsion with good particle size stability under the condition of strong mechanical stirring, and enable the HLB value of the composite surfactant to be matched with the uniform dispersion of an auxiliary agent system.
Comparative examples 6 to 8
The composition ratios of the oil-soluble PVC polymeric emulsion dispersing auxiliary in each comparative example are shown in the following table 2.
Table 2 comparative PVC polymeric emulsion dispersion aid formulation
。
Examples 4 to 8 and comparative examples 9 to 12
The application of the oil-soluble PVC polymerization emulsion dispersion auxiliary agent comprises the following steps: 2.2kg of desalted water is added into a 10L stainless steel pressure reaction kettle provided with two layers of double-leaf flat slurry, oil-soluble PVC polymerization emulsion dispersion auxiliary agent is added proportionally, and then 4.8g of 5% concentration polyvinyl alcohol PVA80 aqueous solution, 5.1g of 3% concentration hydroxypropyl methyl cellulose E50 aqueous solution and 2.75g of 8% concentration polyvinyl alcohol PVA45 oil-soluble solution are added. 0.240g of tert-butyl peroxyneodecanoate with a content of 75% and 0.495g of pivalate peroxide with a content of 75%. Pumping the pressure in the kettle to be lower than minus 0.09MPa, adding 1kg of vinyl chloride monomer, starting stirring, controlling the rotating speed at 470rpm, firstly stirring and mixing for 10-15 min at normal temperature, then raising the temperature of the kettle to 58.3+/-0.2 ℃, and starting timing after the temperature is stable. When the pressure in the kettle was reduced by 0.30MPa, 1g of terminator ATSC was added to the kettle. And continuously controlling the kettle temperature to 58.3+/-0.2 ℃ to terminate the reaction. And (3) recycling unreacted vinyl chloride monomer in the polymerization kettle from the PVC slurry, centrifugally dehydrating the obtained slurry, and drying the slurry in a vacuum drying oven at 60 ℃ and under the pressure of-0.1 MPa for 6 hours to obtain PVC resin powder.
The amounts and types of the oil-soluble PVC polymerization emulsion dispersion aid, the polyvinyl alcohol PVA80, the hydroxypropyl methyl cellulose E50 and the polyvinyl alcohol PVA45 are shown in the table 3 below.
Wherein PVC dispersion aid examples 4-8 are from example 1 and comparative examples 10-12 are from comparative examples 6-8, respectively.
Table 3 use of oil-soluble PVC polymeric emulsion dispersing aid
。
Performance testing
The PVC resin powder obtained in examples 4-8 and comparative examples 9-12 are prepared by the following weight parts:
PVC: organotin TM-181 stabilizer: DOP: lubricant ZB-74=100: 1.2:50:0.4
Weighing 1516 g of total weight, placing the materials into a 10-liter kettle type high-speed mixer, mixing for 15-20 minutes at a rotating speed of 800-1000 r/min, discharging the materials when the temperature of the materials reaches 130-135 ℃, transferring the materials into a cooling mixer, cooling to 45 ℃, taking 200 g of PVC transparent sheet formula materials, opening the materials into sheets with the thickness of 2-3 mm on a 155 ℃ double-roller sheet opening machine for 3 minutes, opening the sheets to cool the sheets to room temperature, cutting and weighing 100g of the sheets, molding the sheets on a hot press with a 2mm mold frame at the temperature of 180 ℃ for 3 minutes, maintaining the pressure for 2 minutes, discharging the sheets, transferring the transparent sheets and the mold frame together onto a cooling tablet machine, continuously maintaining the pressure and cooling for 8 minutes to room temperature, taking out the sheets, cutting the transparent sheets with the thickness of 2mm and the proper area, and detecting the yellow index according to HG/T3862-2006 standard. The transmittance and haze of the PVC transparent sheet are tested according to the national standard GB/T2410-2008. The results of the measurements are shown in Table 4 below.
Table 4 test results
。
From the test results in table 4, it can be seen that the dispersion aids of other components are used, and the indexes such as haze and light transmittance are obviously reduced, so that it can be demonstrated that the effect of synergistically improving the initial coloring performance of the PVC resin after the pentaerythritol tetrakis (3-laurylthiopropionate) and the octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate are compounded is not achieved.
According to examples 6-8 of Table 4, it can be seen that the particle size of the resin is moderate and the particle size distribution is narrowed after the PVC polymerization emulsion dispersion auxiliary agent is added, the whiteness (160 ℃ for 10 min) of the resin is improved compared with that of the original formula (comparative example 9), the plasticizer absorption time is shortened compared with that of the original formula example 12, and three optical performance indexes of the transparent sheet prepared from the PVC resin, namely the light transmittance, the haze and the yellow index, are obviously improved compared with that of the original formula example 12.
From examples 7 and 8 of Table 4, it can be seen that if the PVC polymeric emulsion dispersion aid is used in a small amount, it may result in small particles smaller than 25 μm in the resin of more than 1%, and the particle size distribution of the resin is widened; if the dosage is too much, the total dispersant of the reaction system is too much, the average particle size of the resin is increased to 129 mu m, and the absorption performance of the plasticizer processed after the PVC resin is affected, so that the optical performance of the PVC transparent sample wafer detection is reduced.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (9)
1. An oil-soluble PVC polymerization emulsion dispersion auxiliary agent is characterized in that: comprises the following components in parts by weight: deionized water: 300-350 parts of a lubricant; 3- (dimethylamino) propyl acrylate: 2.8-3.2 parts; polyoxyethylene sorbitan trioleate: 8.8-9.2 parts; pentaethylene glycol: 1.4-1.6 parts; tetraethylene glycol: 2.4-2.6 parts; hydrotalcite: 25-35; stabilizing agent: 23-28 parts of a lubricant; an antioxidant: 40-50 parts of a lubricant.
2. The oil-soluble PVC polymeric emulsion dispersing aid of claim 1, wherein: the stabilizer is prepared from lanthanum acetylacetonate and uracil in a weight ratio of 1.5-2.5: 1, and mixing.
3. The oil-soluble PVC polymeric emulsion dispersing aid of claim 1, wherein: the antioxidant is antioxidant 1076 and antioxidant DLTDP according to the weight ratio of 0.8-1.5: 1, and mixing.
4. The oil-soluble PVC polymeric emulsion dispersing aid of claim 1, wherein: comprises the following components in parts by weight: deionized water: 320 parts; 3- (dimethylamino) propyl acrylate: 3 parts; polyoxyethylene sorbitan trioleate: 9 parts; pentaethylene glycol: 1.5 parts; tetraethylene glycol: 2.5 parts; hydrotalcite: 30; stabilizing agent: 25 parts; an antioxidant: 45 parts.
5. A preparation method of an oil-soluble PVC (polyvinyl chloride) polymerization emulsion dispersion aid is characterized by comprising the following steps of: according to the weight portion ratio of any one of claims 1-4, adding the raw materials into an emulsifying container, heating for dissolving, shearing and emulsifying for 50-70 min to obtain the modified starch.
6. The method for preparing the oil-soluble PVC polymeric emulsion dispersing aid according to claim 5, wherein the method comprises the following steps: and the heating and dissolving step is to heat to 45-50 ℃ for dissolving and stirring uniformly.
7. The method for preparing the oil-soluble PVC polymeric emulsion dispersing aid according to claim 5, wherein the method comprises the following steps: the shear milk is sheared at a high speed of 5500 r/min.
8. The use of the oil-soluble PVC polymeric emulsion dispersing aid according to any one of claims 1 to 4, characterized in that: the ternary dispersion system is applied to ternary dispersion systems with polyvinyl alcohol PVA80, hydroxypropyl methyl cellulose E50 and polyvinyl alcohol PVA45 serving as dispersing agents;
the consumption of the oil-soluble PVC polymerization emulsion dispersing auxiliary is 180-220 ppm relative to the mass content of the VCM monomer.
9. The use of an oil-soluble PVC polymeric emulsion dispersing aid according to claim 8, wherein: the oil-soluble PVC polymerization emulsion dispersion aid according to any one of claims 1 to 4, wherein the oil-soluble PVC polymerization emulsion dispersion aid is mixed with a dispersing agent before polymerization reaction, and then added into a polymerization system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111239921.XA CN116023556B (en) | 2021-10-25 | 2021-10-25 | Oil-soluble PVC (polyvinyl chloride) polymerization emulsion dispersion aid, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111239921.XA CN116023556B (en) | 2021-10-25 | 2021-10-25 | Oil-soluble PVC (polyvinyl chloride) polymerization emulsion dispersion aid, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116023556A CN116023556A (en) | 2023-04-28 |
| CN116023556B true CN116023556B (en) | 2024-05-17 |
Family
ID=86072844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111239921.XA Active CN116023556B (en) | 2021-10-25 | 2021-10-25 | Oil-soluble PVC (polyvinyl chloride) polymerization emulsion dispersion aid, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116023556B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1345353A (en) * | 1999-12-03 | 2002-04-17 | 可乐丽股份有限公司 | Aqueous emulsion and dispersant for suspension polymerization of vinyl compound |
| JP2017061656A (en) * | 2015-09-25 | 2017-03-30 | 日本酢ビ・ポバール株式会社 | Dispersion auxiliary agent for suspension polymerization and its aqueous liquid, and method for producing vinyl resin using them |
| CN108976633A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of Lanthanum Stearate dispersion and preparation method and the application in thermostabilization polyvinyl chloride resin |
-
2021
- 2021-10-25 CN CN202111239921.XA patent/CN116023556B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1345353A (en) * | 1999-12-03 | 2002-04-17 | 可乐丽股份有限公司 | Aqueous emulsion and dispersant for suspension polymerization of vinyl compound |
| JP2017061656A (en) * | 2015-09-25 | 2017-03-30 | 日本酢ビ・ポバール株式会社 | Dispersion auxiliary agent for suspension polymerization and its aqueous liquid, and method for producing vinyl resin using them |
| CN108976633A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of Lanthanum Stearate dispersion and preparation method and the application in thermostabilization polyvinyl chloride resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116023556A (en) | 2023-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4879362A (en) | Modified polytetrafluoroethylene resins | |
| EP2011804A1 (en) | Tetrafluoroethylene polymer and aqueous dispersion thereof | |
| CN110760019B (en) | Vinyl chloride polymerization terminator, preparation method and application thereof | |
| US20110213088A1 (en) | Heat aged perfluoropolymer | |
| CN116023556B (en) | Oil-soluble PVC (polyvinyl chloride) polymerization emulsion dispersion aid, preparation method and application | |
| EP2064284B1 (en) | Composition of at least one vinylidene chloride polymer | |
| EP1279693B1 (en) | A process for obtaining non thermoprocessable fine powders of homopolymer or modified PTFE | |
| KR20110139326A (en) | Method for producing vinyl chloride-based resin paste having reduced change of elapsed time in viscosity | |
| PL188498B1 (en) | Method of obtaining particulate pvc | |
| CN107474167A (en) | Chloroethylene polymerization reaction terminating method | |
| JP5295929B2 (en) | Polyvinylidene chloride resin composition, process for producing the same, and molded article formed from the resin composition | |
| US4547481A (en) | Process for the polymerization of ethylenically unsaturated monomers | |
| CN115536959B (en) | Water-soluble PVC (polyvinyl chloride) polymeric emulsion dispersing agent and preparation method thereof | |
| US4006201A (en) | Process for the production of polyvinyl chloride graft copolymers | |
| JPS584933B2 (en) | Production method of plasticized vinylidene chloride↓-vinyl chloride copolymer | |
| CN105745259B (en) | Vinylidene chloride resin film and its manufacturing method | |
| CN109384874B (en) | Involucra remover for improving porosity of polyvinyl chloride resin and polymerization method | |
| WO2010137718A1 (en) | Polymer fine particles capable of preventing the generation of gum in extrusion molding | |
| US8609771B2 (en) | Process for preparing a vinylidene chloride polymer composition | |
| CZ292745B6 (en) | Process for preparing an aqueous suspension | |
| KR102520197B1 (en) | Method for preparing vinyl chloride polymer | |
| TWI580695B (en) | Chlorinated polyvinyl chloride and the preparation thereof | |
| CN108976336A (en) | A kind of preparation method improving vinyl chloride-vinylidene chloride copolymer polymerization efficiency | |
| KR20170143435A (en) | Method for preparing vinyl chloride polymer | |
| CN107141662A (en) | A kind of preparation method for the polyvinylidene chloride composition for extending the food fresh keeping phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |