CN103087249B - Food packaging latex and its preparation method and application - Google Patents
Food packaging latex and its preparation method and application Download PDFInfo
- Publication number
- CN103087249B CN103087249B CN201210571869.2A CN201210571869A CN103087249B CN 103087249 B CN103087249 B CN 103087249B CN 201210571869 A CN201210571869 A CN 201210571869A CN 103087249 B CN103087249 B CN 103087249B
- Authority
- CN
- China
- Prior art keywords
- latex
- preparation
- mix monomer
- emulsifying agent
- initiator
- 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
- 235000013305 food Nutrition 0.000 title claims abstract description 40
- 239000004816 latex Substances 0.000 title claims abstract description 30
- 229920000126 latex Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 17
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000012856 packing Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- 239000003999 initiator Substances 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 17
- 238000010899 nucleation Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003795 desorption Methods 0.000 claims description 12
- -1 sodium sulfonate compounds Chemical class 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000004200 microcrystalline wax Substances 0.000 claims description 7
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 7
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012785 packaging film Substances 0.000 claims description 5
- 229920006280 packaging film Polymers 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- OVOPQOFZQZDHPJ-UHFFFAOYSA-N COC(CC(C(=O)OC(C(C)C)C)S(=O)(=O)O)=O Chemical class COC(CC(C(=O)OC(C(C)C)C)S(=O)(=O)O)=O OVOPQOFZQZDHPJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 239000008234 soft water Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 6
- 230000003628 erosive effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 238000010556 emulsion polymerization method Methods 0.000 abstract 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 2
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The invention discloses a kind of food packaging latex and its preparation method and application, its with a certain amount of vinylidene chloride, methyl methacrylate, methacrylic acid for mix monomer, select specific seed emulsifying agent and blending emulsifiers, adopt specific seeded emulsion polymerization method to obtain.It can directly be coated on food product packing film base material, without the need to being coated with primer, greatly saves food product pack production cost.By the food product packing film of its coating, there is high barrier, oil-proofness, erosion resistance, guarantor's taste, protection against the tide, mildew-resistant, directly can carry out with food performances such as contacting, fire-retardant, and level of residual monomers is low.This latex stability is excellent.
Description
Technical field
The present invention relates to a kind of latex, especially food packaging latex and its preparation method and application, belongs to novel high polymer material field.
Background technology
Polyvinylidene dichloride (PVDC) is a kind of nonpoisonous and tasteless, safe and reliable high barrier material, polyvinylidene dichloride (PVDC) latex is widely used in food product pack, except the general property with plastics, also there is the protection against the tide of oil-proofness, erosion resistance, guarantor's taste and excellence, mildew-resistant, can directly carry out the performance such as contacting with food, also there is excellent printing performance simultaneously.
Patent CN1535814A discloses a kind of PVDC lamination complex fire resistant cooking food packing film, the copolymer film of middle layer PVDC(vinylidene chloride and vinylchlorid) be connected with the two-layer of both sides respectively by the solvent-free caking agent of bi-component polyurethane ester type, mainly solve the high-barrier of food packaging film, transparent type, resistant to elevated temperatures problem.Patent CN101306743A discloses a kind of milk packaging film, outer membrane is polyvinylidene chloride film, tackiness agent is wherein a kind of in single, double part polyurethane type solvent or adhesive for solvent-free use, the film of inner side is black and white polyethylene film, mainly solves the problems such as material easily absorbs water, barrier is low.
Above-mentioned packaging material for food of the prior art is multi-layer compound structure, needs to arrange binder layer between coating layer and basic unit, to ensure that the packaging film that obtains is indeformable, not ftracture, there is complex manufacturing, equipment requirements is high, the problems such as product price is high.Prior art does not all propose a kind of food packaging latex, only need be coated with this latex when coat foods packaging base material, food product pack can be made to have high barrier, oil-proofness, erosion resistance, guarantor's taste, protection against the tide, mildew-resistant, can directly carry out the performance such as contacting with food.During latex coat foods packaging of the present invention, without the need to being coated with primer, greatly reduce food product pack production cost, and avoid the problem of environmental pollution that existing urethane primer brings; Latex of the present invention has good stability simultaneously, and long storage periods is breakdown of emulsion not, and glue spread is little, is easily coated with, and level of residual monomers is low, manufactures the advantages such as simple.
Summary of the invention
For the above technical problem existed in prior art, the invention provides a kind of food packaging latex coated on polypropylene film and its preparation method and application, its good stability, long storage periods not breakdown of emulsion, glue spread little, be easily coated with, alternative original solvent borne polyurethane primer, security is good, environmental protection, can directly coating on film substrate, without the need to being coated with primer, greatly saving food product pack production cost; This latex preparation method is simple, and working condition is controlled; By the food product packing film of its coating, there is high barrier, oil-proofness, erosion resistance, guarantor's taste, protection against the tide, mildew-resistant, directly can carry out with food performances such as contacting, fire-retardant.
The present invention is achieved by the following technical solutions: food packaging latex, formed by emulsion polymerization way copolymerization by following reaction raw materials, and reaction raw materials and weight part are:
(1) monomer mixture 50 parts, described monomer mixture comprises the vinylidene chloride accounting for mix monomer gross weight 89-92%, the methyl methacrylate accounting for mix monomer gross weight 4-7% and accounts for the methacrylic acid of mix monomer gross weight 4-7%;
(2) initiator, described initiator comprises: organo-peroxide 0.04-0.12 part and sodium formaldehyde sulphoxylate 0.04-0.12 part;
(3) seeding polymerization emulsifying agent, described seeding polymerization emulsifying agent comprises and is selected from sodium sulfonate compounds any one 0.06 part and MA-80(chemistry sulfo-succinic acid methyl-isobutyl methyl esters salt by name, or is called succinic acid dihexyl sodium sulfonate) 0.14 part;
(4) blending emulsifiers, described blending emulsifiers comprises AMPS(chemistry 2-acrylamide-2-methylpro panesulfonic acid by name) 0.6 part and 2A-1 emulsifying agent (chemistry alkyl diphenyl ether disulfonate by name, commodity are called DOWFAX8390, or DOWFAX30599) 0.5 part;
(5) auxiliary agent, described auxiliary agent comprises ammonium acetate 0.012 part and iron protochloride 0.0005 part.
Preferably, in described initiator, organo-peroxide is tertbutyl peroxide; In described seeding polymerization emulsifying agent, sodium sulfonate compounds is Sodium dodecylbenzene sulfonate.
The present invention also provides the preparation method of described food packaging latex, and adopt the preparation of seeding polymerization method, concrete preparation process comprises:
(1) mix monomer preparation: stir 2h by after described vinylidene chloride, methacrylic ester mixing, for subsequent use;
(2) blending emulsifiers preparation: after described AMPS, 2A-1 emulsifying agent, methacrylic acid mixing, be diluted with water to 10 parts, high-speed stirring mixes, for subsequent use;
(3) initiator preparation: it is 2% that described two kinds of initiators are diluted to mass percentage concentration respectively, for subsequent use;
(4) Seeded polymerization: deionized water or soft water 32 parts, described auxiliary agent, described seeding polymerization emulsifying agent are added in reactor, envelope still, with nitrogen replacement 3 times, vacuumizes, suck the mix monomer accounting for the mix monomer gross weight 5% that step 1 prepares, cold dispersion 0.5h, is warming up to 47 DEG C, is continuously pumped into the initiator prepared with the speed of 8kg/48h, controlling temperature of reaction is 55 DEG C, when Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
(5) letex polymerization: the speed added with 16h is continuously pumped into the obtained remaining mix monomer of blending emulsifiers that step 2 prepares, step 1, as Pressure Drop to 0 ~-0.01MPa, reaction terminates, and adds microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C and keeps 1h, and bottom valve is crack, desorption 2h, then add the water vapor of 0.1MPa, filter, obtain copolymer emulsion.
The present invention also provides the application of described food packaging latex in coating food packaging film.
The present invention also provides the food product packing film applying described food packaging latex.
Emulsion of the present invention adds reactive emulsifier in blending emulsifiers, improves emulsion intercalation method; Further, monomer methacrylic acid together added in letex polymerization stage and reactive emulsifier, due to vinylformic acid good water solubility, it is good to the parcel of emulsifying agent, obtained polymkeric substance even particle size distribution, good emulsion stability, deposits 2 years not breakdown of emulsion, effects without precipitation under can reaching normal temperature.In addition, obtained emulsion tackiness is good, when not being coated with primer, directly can coat on the film substrates such as food product packing film, replacing existing urethane primer.
In preparation method of the present invention, have employed specific feed time and process control parameter, with the addition of auxiliary agent ammonium acetate, make the emulsion prepared have satisfactory stability; Further, before vacuum desorption step, add microcrystalline wax, froth breaking effect can be played, improve vacuum desorption effect, thus reduce level of residual monomers, and after cooling, microcrystalline wax is solid-state, can be recycled by filtration.
The present invention can obtain the copolymer latex that solid content is about 50%, can coat on polypropylene film, for food product pack.This latex stability is good, long storage periods not breakdown of emulsion, glue spread little, be easily coated with, security is good, environmental protection, greatly saves food product pack production cost; This latex preparation method is simple, and working condition is controlled; By the food product packing film of its coating, there is high barrier, oil-proofness, erosion resistance, guarantor's taste, protection against the tide, mildew-resistant, directly can carry out with food performances such as contacting, fire-retardant.
Obtained emulsion can measure with following methods:
| Mensuration project | Testing method |
| Solid content, % | GB1725-79 |
| Surface tension, mN/m | GB1725-79 |
| Viscosity, mPas | U.S. BROOKFIELD viscometer |
| PH value | The accurate pH meter of PHS-3C |
| Density, g/cm 3 |
Latex glue spread of the present invention is single painting 3.2g/ ㎡, is measured, steam penetrating capacity≤6g/ ㎡ 24h by the BOPP food product packing film of its coating according to standard GB/T1037 condition B; Measure according to standard GB/T19789-2005 voltameter detection method, oxygen transit dose≤18g/ ㎡ 24h; Measure according to standard GB/T5009.122-2003, vinylidene chloride monomer residual quantity≤1mg/kg or do not detect.
Accompanying drawing explanation
Fig. 1 is technological process block-diagram of the present invention.
Embodiment
Embodiment 1
(1) mix monomer preparation: stir 2h after vinylidene chloride 89kg, methyl methacrylate 5kg being mixed, for subsequent use;
(2) mixed polymerization emulsifying agent preparation: after AMPS1.2kg, 2A-1 emulsifying agent 1kg, methacrylic acid 6kg being mixed, be diluted with water to 20kg, high-speed stirring mixes, for subsequent use;
(3) initiator preparation: it is 2% that tertbutyl peroxide 80g, sodium formaldehyde sulphoxylate 80g are diluted to mass percentage concentration respectively, for subsequent use;
(4) Seeded polymerization: deionized water 64kg, auxiliary agent ammonium acetate 20g, iron protochloride 1g, seeding polymerization emulsifying agent Sodium dodecylbenzene sulfonate 120g, MA-80280g are added in 200L reactor, envelope still, with nitrogen replacement 3 times, vacuumize, suck 5%(weight) the obtained mix monomer of step 1, cold dispersion 0.5h, be warming up to 47 DEG C, the initiator prepared is continuously pumped into the speed of 8kg/48h, controlling temperature of reaction is 55 DEG C, when Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
(5) letex polymerization: the speed added with 16h is continuously pumped into the obtained remaining mix monomer of blending emulsifiers that step 2 prepares, step 1, as Pressure Drop to 0 ~-0.01MPa, reaction terminates, and adds microcrystalline wax 100g, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C and keeps 1h, and bottom valve is crack, desorption 2h, then add the water vapor of 0.1MPa, filter, obtain copolymer emulsion.
Obtained emulsion parameter is as follows:
Solid content (%): 50
Surface tension (mN/m): 40
Viscosity (mPas): 10
PH value: 1.5
Density (g/cm
3): 1.23
Single obtained emulsion of 3.2g/ ㎡ that is coated with is in BOPP film, and measure according to standard GB/T1037 condition B, steam penetrating capacity is 6g/ ㎡ 24h; Measure according to standard GB/T19789-2005 voltameter detection method; Oxygen transit dose is 18g/ ㎡ 24h; Measure according to standard GB/T5009.122-2003, do not detect residual vinylidene chloride monomer.
Embodiment 2
(1) mix monomer preparation: stir 2h after vinylidene chloride 92kg, methyl methacrylate 4kg being mixed, for subsequent use;
(2) mixed polymerization emulsifying agent preparation: after AMPS1.2kg, 2A-1 emulsifying agent 1kg, methacrylic acid 4kg being mixed, be diluted with water to 20kg, high-speed stirring mixes, for subsequent use;
(3) initiator preparation: it is 2% that tertbutyl peroxide 80g, sodium formaldehyde sulphoxylate 80g are diluted to mass percentage concentration respectively, for subsequent use;
(4) Seeded polymerization: deionized water 64kg, auxiliary agent ammonium acetate 20g, iron protochloride 1g, seeding polymerization emulsifying agent Sodium dodecylbenzene sulfonate 120g, MA-80280g are added in 200L reactor, envelope still, with nitrogen replacement 3 times, vacuumize, suck 5%(weight) the obtained mix monomer of step 1, cold dispersion 0.5h, be warming up to 47 DEG C, the initiator prepared is continuously pumped into the speed of 8kg/48h, controlling temperature of reaction is 55 DEG C, when Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
(5) letex polymerization: the speed added with 16h is continuously pumped into the obtained remaining mix monomer of blending emulsifiers that step 2 prepares, step 1, as Pressure Drop to 0 ~-0.01MPa, reaction terminates, and adds microcrystalline wax 100g, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C and keeps 1h, and bottom valve is crack, desorption 2h, then add the water vapor of 0.1MPa, filter, obtain copolymer emulsion.
Embodiment 3
(1) mix monomer preparation: stir 2h after vinylidene chloride 90kg, methyl methacrylate 6kg being mixed, for subsequent use;
(2) mixed polymerization emulsifying agent preparation: after AMPS1.2kg, 2A-1 emulsifying agent 1kg, methacrylic acid 4kg being mixed, be diluted with water to 20kg, high-speed stirring mixes, for subsequent use;
(3) initiator preparation: it is 2% that tertbutyl peroxide 80g, sodium formaldehyde sulphoxylate 80g are diluted to mass percentage concentration respectively, for subsequent use;
(4) Seeded polymerization: deionized water 64kg, auxiliary agent ammonium acetate 20g, iron protochloride 1g, seeding polymerization emulsifying agent sodium laurylsulfonate 120g, MA-80280g are added in 200L reactor, envelope still, with nitrogen replacement 3 times, vacuumize, suck 5%(weight) the obtained mix monomer of step 1, cold dispersion 0.5h, be warming up to 47 DEG C, the initiator prepared is continuously pumped into the speed of 8kg/48h, controlling temperature of reaction is 55 DEG C, when Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
(5) letex polymerization: the speed added with 16h is continuously pumped into the obtained remaining mix monomer of blending emulsifiers that step 2 prepares, step 1, as Pressure Drop to 0 ~-0.01MPa, reaction terminates, and adds microcrystalline wax 100g, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C and keeps 1h, and bottom valve is crack, desorption 2h, then add the water vapor of 0.1MPa, filter, obtain copolymer emulsion.
Claims (3)
1. a preparation method for food packaging latex, is characterized in that:
This latex is formed by emulsion polymerization way copolymerization by following reaction raw materials, and reaction raw materials and weight part are:
(1) monomer mixture 50 parts, described monomer mixture comprises the vinylidene chloride accounting for mix monomer gross weight 89-92%, the methyl methacrylate accounting for mix monomer gross weight 4-7% and accounts for the methacrylic acid of mix monomer gross weight 4-7%;
(2) initiator, described initiator comprises: organo-peroxide 0.04-0.12 part and sodium formaldehyde sulphoxylate 0.04-0.12 part;
(3) seeding polymerization emulsifying agent, described seeding polymerization emulsifying agent comprises any one 0.06 part and sulfo-succinic acid methyl-isobutyl methyl esters salt 0.14 part being selected from sodium sulfonate compounds;
(4) blending emulsifiers, described blending emulsifiers comprises 2-acrylamide-2-methylpro panesulfonic acid 0.6 part and alkyl diphenyl ether disulfonate 0.5 part;
(5) auxiliary agent, described auxiliary agent comprises ammonium acetate 0.012 part and iron protochloride 0.0005 part;
In described initiator, organo-peroxide is tertbutyl peroxide;
In described seeding polymerization emulsifying agent, sodium sulfonate compounds is Sodium dodecylbenzene sulfonate;
Its concrete preparation process comprises:
(1) mix monomer preparation: stir 2h by after described vinylidene chloride, methacrylic ester mixing, for subsequent use;
(2) blending emulsifiers preparation: after described 2-acrylamide-2-methylpro panesulfonic acid, alkyl diphenyl ether disulfonate, methacrylic acid mixing, be diluted with water to 10 parts, high-speed stirring mixes, for subsequent use;
(3) initiator preparation: it is 2% that described two kinds of initiators are diluted to mass percentage concentration respectively, for subsequent use;
(4) Seeded polymerization: deionized water or soft water 32 parts, described auxiliary agent, described seeding polymerization emulsifying agent are added in reactor, envelope still, with nitrogen replacement 3 times, vacuumizes, suck the mix monomer accounting for the mix monomer gross weight 5% that step 1 prepares, cold dispersion 0.5h, is warming up to 47 DEG C, is continuously pumped into the initiator prepared with the speed of 8kg/48h, controlling temperature of reaction is 55 DEG C, when Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
(5) letex polymerization: the speed added with 16h is continuously pumped into the obtained remaining mix monomer of blending emulsifiers that step 2 prepares, step 1, as Pressure Drop to 0 ~-0.01MPa, reaction terminates, and adds microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C and keeps 1h, and bottom valve is crack, desorption 2h, then add the water vapor of 0.1MPa, filter, obtain copolymer emulsion.
2. according to the application of food packaging latex in coating food packaging film prepared by the method described in claim 1.
3. apply the food product packing film of the food packaging latex prepared according to the method described in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210571869.2A CN103087249B (en) | 2012-12-26 | 2012-12-26 | Food packaging latex and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210571869.2A CN103087249B (en) | 2012-12-26 | 2012-12-26 | Food packaging latex and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103087249A CN103087249A (en) | 2013-05-08 |
| CN103087249B true CN103087249B (en) | 2015-12-23 |
Family
ID=48200410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210571869.2A Active CN103087249B (en) | 2012-12-26 | 2012-12-26 | Food packaging latex and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103087249B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294913B (en) * | 2015-11-25 | 2017-04-19 | 海南赛诺实业有限公司 | PVDC copolymerization emulsion for flame-retardant carpets, preparation method and applications thereof |
| CN114349895A (en) * | 2022-01-13 | 2022-04-15 | 万华化学集团股份有限公司 | Antibacterial, antioxidant and beatable barrier coating resin for food packaging and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4350622A (en) * | 1980-02-15 | 1982-09-21 | Asahi-Dow Limited | Aqueous dispersions of vinylidene chloride resins |
| US4694068A (en) * | 1984-10-01 | 1987-09-15 | The Dow Chemical Company | Method for the preparation of a vinylidene chloride interpolymer film |
| CN1178223A (en) * | 1997-04-26 | 1998-04-08 | 浙江大学 | Preparation of metachloroethylene copolymer latex |
| CN101186666A (en) * | 2007-11-19 | 2008-05-28 | 上海氯碱化工股份有限公司 | Method for preparing polyvinylidene chloride and acrylic ester copolymerization latex |
| CN101358054A (en) * | 2008-09-04 | 2009-02-04 | 葛飞雄 | High barrier food package coated membrane latexes by thermal sealing at low temperature and preparation method |
-
2012
- 2012-12-26 CN CN201210571869.2A patent/CN103087249B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4350622A (en) * | 1980-02-15 | 1982-09-21 | Asahi-Dow Limited | Aqueous dispersions of vinylidene chloride resins |
| US4694068A (en) * | 1984-10-01 | 1987-09-15 | The Dow Chemical Company | Method for the preparation of a vinylidene chloride interpolymer film |
| CN1178223A (en) * | 1997-04-26 | 1998-04-08 | 浙江大学 | Preparation of metachloroethylene copolymer latex |
| CN101186666A (en) * | 2007-11-19 | 2008-05-28 | 上海氯碱化工股份有限公司 | Method for preparing polyvinylidene chloride and acrylic ester copolymerization latex |
| CN101358054A (en) * | 2008-09-04 | 2009-02-04 | 葛飞雄 | High barrier food package coated membrane latexes by thermal sealing at low temperature and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103087249A (en) | 2013-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101186666A (en) | Method for preparing polyvinylidene chloride and acrylic ester copolymerization latex | |
| EP2580254B1 (en) | Multistage preparation of aqueous polymer dispersions for producing composite films | |
| CN103059197B (en) | Aqueous antiseptic metal undercoat polyvinyl dichloride (PVDC) copolymer emulsion and preparation method thereof and application | |
| CN104293245A (en) | Vinyl acetate wood adhesive and preparation method thereof | |
| CN105294947A (en) | Preparing method for high-performance styrene-butadiene latex for papermaking | |
| NO147031B (en) | PROCEDURE FOR THE PREPARATION OF DISPERSIBLE DISPERSION POWDER AND USE OF THESE AS A BINDING AGENT | |
| CN103087249B (en) | Food packaging latex and its preparation method and application | |
| CN108084370A (en) | A kind of low-temperature heat-sealing EVA lotions and its preparation method and application | |
| EP3230519B1 (en) | Water redispersible polymeric powder for carpet coating compositions | |
| CN106674412B (en) | A kind of 1,1- fluoride polymer and preparation method thereof | |
| US20120316282A1 (en) | Vinyl ester/ethylene copolymer dispersions for use in adhesive formulations | |
| CN105524531A (en) | PP substrate base-coating paint composition and preparation method thereof | |
| CN103059202A (en) | Polyvinylidene chloride copolymer emulsion for pharmaceutical packing coating and preparation method and application thereof | |
| CN103725230B (en) | Adhesive dispersion is used for the purposes of frlml laminating | |
| CN108102472A (en) | A kind of film low-temperature heat-sealing coating and preparation method thereof | |
| CN101522724A (en) | Process for preparing an aqueous polymer dispersion | |
| CN103044603B (en) | Food packaging latex and its preparation method and application | |
| CN102977249B (en) | Chloroethylene-isooctyl acrylate copolymer emulsion and preparation method thereof | |
| CN105408441B (en) | Mending agent for tyre | |
| CN110922519A (en) | Vinyl chloride and acrylic acid copolymer emulsion and preparation method thereof | |
| CN103059193A (en) | Polyvinyl dichloride (PVDC) coating latex special for cigarette films and preparation method and application thereof | |
| CN108485399A (en) | A kind of coating PVDC water-based emulsions | |
| CN103059196B (en) | Polyvinyl dichloride (PVDC) latex for ultrahigh-resistance diaphragm used for food packaging and preparation method thereof and application thereof | |
| CN102993849B (en) | VCM (Vinyl Chloride Monomer)-2-EHA (ethylhexyl acrylate)-organosilicone copolymerization emulsion and preparation method thereof | |
| US20220177726A1 (en) | Gas barrier composition, coating agent, and laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 571152, No. 18, North Light Road, Lion Industrial Park, Haikou national hi tech Zone, Hainan Applicant after: Hainan Bikai Waterborne Coatings Co., Ltd. Address before: 570125 Hainan city in Haikou Province, North Longkun Road No. 2 Park building 19 floor Applicant before: Hainan Bikai Waterborne Coatings Co., Ltd. |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20151104 Address after: 571152, No. 18, North Light Road, Lion Industrial Park, Haikou national hi tech Zone, Hainan Applicant after: Hainan Bikai Waterborne Coatings Co., Ltd. Address before: 571152, No. 18, North Light Road, Lion Industrial Park, Haikou national hi tech Zone, Hainan Applicant before: Hainan Bikai Waterborne Coatings Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 571152, No. 18, North Light Road, Lion Industrial Park, Haikou national hi tech Zone, Hainan Patentee after: HAINAN JUNENG INNOVATION SERVICES CO., LTD. Address before: 571152, No. 18, North Light Road, Lion Industrial Park, Haikou national hi tech Zone, Hainan Patentee before: Hainan Bikai Waterborne Coatings Co., Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20200416 Address after: 571100 No. 18 North Photovoltaic Road, Shiziling Industrial Park, Xiuying District, Haikou City, Hainan Province Patentee after: HAINAN HAIDAFENG INDUSTRIAL Co.,Ltd. Address before: 571152, No. 18, North Light Road, Lion Industrial Park, Haikou national hi tech Zone, Hainan Patentee before: HUNAN JUNENG INNOVATIVE SERVICE Co.,Ltd. |
|
| TR01 | Transfer of patent right |