CN102952303A - Preparation method of environmentally-friendly powdery chloroprene rubber having characteristics of quick dissolving and high bonding - Google Patents
Preparation method of environmentally-friendly powdery chloroprene rubber having characteristics of quick dissolving and high bonding Download PDFInfo
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Abstract
A preparation method of an environmentally-friendly powdery chloroprene rubber having the characteristics of quick dissolving and high bonding comprises the following steps: 1, adding water and starch into a reaction bottle, reacting at 25-40DEG C, alternatively adding an alkaline solution and a diacid in a dropwise manner, adjusting the pH value to 7-8 when the pH value slowly changes, and carrying out heat insulation to prepare modified starch; 2, adding a polychloroprene latex, water, the modified starch, isoprene, a molecular weight adjusting agent, an initiator and an activator into a polymerization kettle, carrying out a graft polymerization reaction at 25-50DEG C, and adding a terminator when the polymerization conversion rate is 65-75% to prepare a grafted latex; and 3, adding the grafted latex into a condensation kettle, adding an isolation agent, a flocculating agent and a condensation agent, stirring, heating, slaking, dehydrating, and drying to obtain the environmentally-friendly powdery chloroprene rubber having the characteristics of quick dissolving and high bonding. The powder particle size, the powdering rate, the ash content, the volatile matter content, the swelling time, the dissolving time and the peeling strength of the prepared powdery chloroprene rubber are 0.40-0.90mm, not less than 99.5%, not more than 0.09%, not more than 0.15%, 2-15s, 1-3h and not less than 87N/cm respectively.
Description
Technical field
The invention belongs to the preparation of powdered polychloroprene rubber, relate to adhesive field, particularly relate to the instant solution of a class, high bonding, environment-friendly type powdered polychloroprene rubber and preparation method thereof.
Background technology
The binding type chloroprene rubber is the important source material of tackiness agent industry.Because its excellent performance, its Application Areas be from all multi-usages such as building, building materials, mining material, automobile safety capsule and even civilian goods, and still constantly expanding range of application.The binding type powdered polychloroprene rubber is compared with traditional sheet glue, has energy-saving and cost-reducing, as the to improve production process advantages such as automatic control level.
Starch is a kind of reproducible natural biomass macromolecular compound, and raw material sources are abundant and cheap, are a kind of biodegradable renewable resource.Starch (molecular formula: be to be formed by connecting through sugared key by many dehydrated glucose units (C6H10O5) n), on C2, the C3 of each glucose unit and C5, a hydroxyl is arranged respectively, thereby on a starch chain high-polymer molecular thousands of activity hydroxies are just arranged, and each starch granules is interweaved with the form in crystallizing field and unsetting district by unnumbered amylose starch and amylopectin molecular chain and forms.To the powder neoprene, not only improved the adhesive property of sizing agent with starch-grafted, and improved dissolution rate, broadened application scope, more environmental protection.
CN03100424.5 carries out gelatinization with starch, directly condense with polymer latex, polymer emulsion is nature rubber latex, SBR emulsion, neoprene latex, acrylonitrile-butadiene rubber latex, carboxy nitrile rubber emulsion, polyvinyl chloride emulsion, ethylene-vinyl acetate emulsion or polyacrylate dispersion, and the mixture of preparation is mainly used in rubber industry and environment-friendly material.(2007,54 volumes, 197-202) adopt phenolic resin modified starch, and then treated starch and styrene-butadiene latex blend are condensed altogether at 4 phases Qi Qing etc. for " research of Starch/SBR Composites structure and performance ", rubber industry.Zhang Jing etc. are at " application of environmental protection starch adhesive on timber " (Heilungkiang ecological engineering Professional School journal, 2009,22 volumes, 1 phase, introduced grafting modified of starch adhesive for wood and starch esterification/copolymerization adhesive for wood 53-55), graft copolymerization reagent commonly used has polyvinyl alcohol, polyacrylamide, polyacrylic acid, epoxy chloropropane etc.Liu Guang far waits (" utilizing the research of production of corn starch water tolerance odorless sizing agent ", forest product industry, 1999,26 volumes, 13-16) make W-Gum and diprotic acid generation part esterification at 6 phases, add the stablizer water soluble polymer, make starch adhesive host.Add industrial flour during impregnation, solid content is reached more than 45%, then add the linking agent isocyanate compound, be water-resisting type corn odorless sizing agent.Strength of Plywood meets II class plywood character index request.Shi Junyou (" utilizing the esterification of W-Gum to make the research of API sizing agent ", Beihua University's journal (natural science edition), 2004,5 volumes, 4 phases are 361-364) with diprotic acid and W-Gum generation part esterification, under the condition that the stablizer polyoxyethylene glycol exists, add carboxy nitrile rubber latex and esterification W-Gum mixing copolymerization, make starch adhesive host.Add POV barium as filler, polyisocyanate compound adds hydrosulphite as the encapsulant of temporary transient blocked isocyanate group simultaneously as linking agent, effectively prolongs the working life of sizing agent.The timber-works such as the glued board of its mongolicum Turcz. with Modified Starch Adhesive compacting, core-board all reach standard.
The rubber components of a kind of pneumatic tire that US2004122134 relates to has starch or softening agent and rubber gels, starch/rubber gels weight ratio approximately 10: 1～1: 10.JP02263882A is for obtaining a kind of tackiness agent of high adhesion, available epoxy, vinyl acetate fat, urea, phenolic aldehyde, polyester, butyronitrile product rubber, silicon rubber, starch, protein and natural rubber etc. are made the nuclei of crystallization as the main body of tackiness agent with zinc oxide.Contain the components such as rubber, polysaccharide and carbon black in a kind of rubber combination that JP2009073981 introduces.GB1532886 has introduced the graftomer of the graft copolymerizations such as a kind of starch and vinyl cyanide, chloroprene rubber.
Summary of the invention
The object of the invention is to adopt direct cohesion pulverizing technology to prepare instant solution, high bonding, environment-friendly type powdered polychloroprene rubber.The preparation method of powdered polychloroprene rubber of the present invention is:
1) modification of starch: take starch as 100 mass parts, in reaction flask, add 60～500 parts of water and 100 parts of starch, stir, heat, temperature of reaction is controlled at 25～40 ℃, drips alkali lye, makes reacting liquid pH value be raised to 10～12, dripping diprotic acid makes the pH value drop to 7 again, alkali lye and diprotic acid alternately drip, until diprotic acid drips fully, the add-on of diprotic acid is 15～30 parts, when the variation of question response liquid pH value is slow, add alkali lye, regulating the pH value is 7～8 again, insulation 40～70min, then the blowing of lowering the temperature makes treated starch;
2) preparation of graft latex: take polychloroprene latex as 100 mass parts, in polymeric kettle, add successively 100 parts of solid contents and be 25%～40% polychloroprene latex, 50～160 parts of water, 5～20 portions of treated starches, 5～20 parts of isoprene, 0.2～1.4 parts of molecular weight regulators, behind nitrogen replacement, stir, heat, treat to add 0.2～1.2 part of initiator and 3～10 parts of activators when the polymeric kettle temperature reaches 15～25 ℃, carry out graft polymerization reaction at 25～50 ℃, when polymerisation conversion reaches 65%～75%, add 2～10 parts of terminators, make graft latex;
3) condensation powdering: get 100 parts of graft latexes and add the cohesion still, under 10～30 ℃ of condensation temperatures, add 4～16 portions of separants, 4～16 parts of flocculation agents, 4～16 parts of flocculation agent, fully mix, be warming up to 20～60 ℃ of slakings 4～6 hours, then make speed through separation, dehydration, drying and separate molten high bonding environment-friendly type powdered polychloroprene rubber.
Starch is various starch among the present invention, such as yam starch, sweet potato starch, tapioca (flour), W-Gum, wheat starch, green starch, and preferred W-Gum.
Owing to when amidin leaves standstill after being stirred into cream, having starch and slowly precipitating, be the stability problem of solution starch water-in-oil emulsion, and further improve its binding property, the present invention need to carry out modification to starch.The consumption of water is 60～500 parts in the starch conversion process, and starch water miscible liquid concentration is 20%～60%, 200～300 parts of preferably water consumptions.
The starch conversion temperature is controlled at 25～40 ℃ among the present invention, preferred 30～35 ℃.
The acid that starch conversion is used among the present invention is diprotic acid, such as oxalic acid, carbonic acid etc., and preferred oxalic acid, mass percentage concentration is 60%～90%, is preferably 70%～80%.The diprotic acid add-on is not enough, and the esterification of W-Gum is also not enough, and has precipitation to form; And the diprotic acid add-on is too much, the starch excessive degradation, and long easily generation storage period starch suspension liquid gelatin phenomenon, the add-on of diprotic acid is 15～30 parts among the present invention, preferred 15～20 parts.
The alkali lye that starch conversion is used among the present invention is alkali or alkali salt or its complex liquid, and such as sodium hydroxide, trolamine, potassium hydroxide etc. and complex liquid thereof, the alkali lye mass percentage concentration is 20%～40%, preferred 25%～35%.Preferred sodium hydroxide and trolamine complex liquid.
Starch conversion alkali lye and diprotic acid alternately drip among the present invention, namely add alkali lye and make pH be raised to 10～12, add diprotic acid again and make pH drop to 7, until diprotic acid drips fully.When reaction was tending towards finishing, the pH value changed slowly, adds alkali lye again, and regulating the pH value is 7～8.
Insulation 40～70min after the starch conversion reaction is finished among the present invention, the blowing of then lowering the temperature.
In the preparation process of graft latex of the present invention, in order to guarantee higher percentage of grafting, in 100 parts of polychloroprene latexs, need to add 50～160 parts of WATER AS FLOW MEDIUM, the mass concentration of control graft latex is 25%～35%.
The treated starch consumption is 5～20 parts in the preparation process of graft latex, preferred 10～15 parts; The isoprene consumption is 5～20 parts, preferred 10～15 parts.
The molecular weight regulator that adopts in the preparation process of graft latex is sulphur or conditioning agent fourth, is 0.2～1.4 part, preferred 0.6～1.0 part; The initiator that adopts both can use water-soluble inorganic peroxide thermolysis type initiator, also can use the oxidation-reduction initiator that is formed by water-soluble inorganic peroxide and reductive agent, for making the good powder-product of crystal property, the oxidation-reduction initiator that is preferably formed by water-soluble inorganic peroxide and reductive agent, consumption is 0.2～1.2 part, is selected from persulphate-hydrosulphite redox initiator, oxymuriate-hydrosulphite redox initiator, hydrogen peroxide-ferrous salt redox initiator.
Activator is selected from rosined soap, petroleum sodium sulfonate, formaldehyde-naphthalene 5 sulfonic acid condenses sodium salts among the present invention, and preferred rosined soap is 3～10 parts.
The graft latex polymerization temperature is 25～50 ℃ among the present invention, preferred 30～40 ℃.
The graft polymerization conversion rate control is 65%～75%, for reducing gel content, preferred 65%～70% among the present invention.
Terminator is selected phthalic acid dibutyl ester among the present invention, and consumption is 2～10 parts.
The present invention is selected from disproportionated rosin soap, fatty acid soaps etc. take soap as separant, preferred disproportionated rosin soap, and consumption is 4～16 parts, preferred 5～10 parts.
Take mineral acid as flocculation agent, be selected from sulfuric acid, hydrochloric acid etc. among the present invention, preferably sulfuric acid, consumption are 4～16 parts, preferred 5～10 parts.
Take the mineral acid sodium salt as flocculation agent, be selected from sodium sulfate, sodium-chlor etc. among the present invention, preferred sodium-chlor, mass concentration is 15%～20%, per 100 parts of graft latex consumptions are 4～20 parts, preferred 5～10 parts.
Among the present invention in the condensation powdering process powder particle curing temperature be 20～60 ℃, preferred 40～50 ℃, the curing time is 4～6 hours.
Prepared instant solution, the high bonding environment-friendly type powdered polychloroprene rubber of the present invention has following feature: powder diameter 0.40mm～0.90mm, powder formation rate 〉=99.5%, ash content≤0.09%, fugitive constituent≤0.15%, swelling time 2～15 seconds, dissolution time 1～3 hour, stripping strength 〉=87N/cm.
Adopt the prepared powdered polychloroprene rubber of present method, have following advantage:
(1) starch and polychloroprene latex, isoprene generation graft crosslinking have improved solvability and the cohesive force of sizing agent.Starch has latex again and strengthens the property both as the part of sizing agent, makes sizing agent have higher clinging power and water tolerance.
(2) starch source is abundant, has the advantages such as quality is light, pollution-free without burn into, raw material is easy to get, cheap, easy to use, has reduced the production cost of sizing agent.
(3) powdered cohesion process of the present invention is stable, reliable, easy, and itself is sizing agent starch, and separant and flocculation agent add-on are less, so that the nonrubber component content is lower in the product, performance is better.
When (4) powdered rubber of the present invention's preparation uses as sizing agent, have the part advantage of starch adhesive, strengthened the advantage of neoprene sizing agent, enlarged range of application.
(5) treated starch and isoprene generation graft polymerization, so that isoprene more easily is condensed into trans isoprene, the kindliness of trans isoprene molecular chain is so that the easier condensation powdering of graft latex.
(6) interaction of treated starch and isoprene, so that sizing agent has been concentrated advantage separately, performance is more good.
(7) the powdered polychloroprene rubber particle diameter of the present invention's preparation is even, be 0.4～0.8mm, and the powder formation rate of graft latex can reach more than 99.5%.
(8) adopting the powdered polychloroprene rubber several seconds of the inventive method preparation is swellable, can dissolve fully in 2 hours, and stripping strength can reach more than the 90N/cm.Need 3～5 hours and the sheet peptization is swollen, (needing to stir) just can finish dissolving in 6～12 hours.
Embodiment
Preparation method to binding type powdered polychloroprene rubber of the present invention is described in further detail below by specific embodiment.
Polychloroprene latex: domestic polychloroprene latex CR244, total solid content are 30%～40%.Isoprene, starch and other reagent are commercially available industrial goods.
Embodiment 1
1. the modification of starch: in reaction flask, add 100 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 25 ℃, drip mass percentage concentration and be 20% sodium hydroxide and the compound alkali lye of trolamine (sodium hydroxide and trolamine mass ratio are 1: 1), make the pH value be elevated to 10, drip again mass percentage concentration and be 60% oxalic acid, make the pH value drop to 7, alkali lye and oxalic acid alternately drip, until 15 parts oxalic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 8, insulation 50min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 100 parts of water, 100 parts of solid contents are 35% polychloroprene latex, add successively 10 parts of isoprene, 12 portions of treated starches, 0.5 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.5 part of Potassium Persulphate when the polymeric kettle temperature reaches 25 ℃ and 3 parts of rosined soaps carry out graft polymerization reaction at 40 ℃.When polymerisation conversion is 70%, add 5 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 25 ℃ of condensation temperatures, add 10 parts of disproportionated rosin soaps, 8 part 15% sulfuric acid, 8 part 15% sodium-chlor fully mixes; Be warmed up to 50 ℃, slaking 6 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.Adopt classical way specimen structure and performance, the result is as follows: powder diameter 0.40mm～0.90mm, powder formation rate 99.8%, ash content 0.09%, fugitive constituent 0.15%, swelling time several seconds, dissolution time 1.5 hours, stripping strength 90N/cm.
Comparative Examples 1
Do not add isoprene and treated starch, testing is that cohesion is tested, and condition is with embodiment 1, experimentation is: get 100 parts of latex and add in the cohesion still, add 10 parts of disproportionated rosin soaps, 8 part 15% sulfuric acid under 25 ℃ of condensation temperatures, 8 part 15% sodium-chlor fully mixes; Be warmed up to 50 ℃, slaking 6 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.The result is as follows: powder diameter 0.30mm～1.50mm, powder formation rate 70%, ash content 0.18%, fugitive constituent 0.25%, tens of seconds of swelling time, dissolution time 3 hours, stripping strength 65N/cm.
Embodiment 2
1. the modification of starch: in reaction flask, add 300 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 40 ℃, drip mass percentage concentration and be 30% sodium hydroxide and the compound alkali lye of trolamine (sodium hydroxide and trolamine mass ratio 1: 2), make the pH value be elevated to 11, drip again mass percentage concentration and be 70% oxalic acid, make the pH value drop to 7, alkali lye and oxalic acid alternately drip, until 20 parts oxalic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 60min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 100 parts of water, 100 parts of solid contents are 30% polychloroprene latex, add successively 20 parts of isoprene, 10 portions of treated starches, 0.6 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.9 part of Potassium Persulphate when the polymeric kettle temperature reaches 15 ℃ and 4 parts of rosined soaps carry out graft polymerization reaction at 35 ℃.When polymerisation conversion is 70%, add 8 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 35 ℃ of condensation temperatures, add 12 parts of disproportionated rosin soaps, 10 part 20% sulfuric acid, 10 part 25% sodium-chlor fully mixes; Be warmed up to 60 ℃, slaking 5 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.Adopt classical way specimen structure and performance, the result is as follows: powder diameter 0.40mm～0.90mm, powder formation rate 99.5%, ash content 0.06%, fugitive constituent 0.12%, swelling time several seconds, dissolution time 1.5 hours, stripping strength 88N/cm.
Comparative Examples 2
Do not add isoprene and treated starch.Experiment is the cohesion experiment, and condition is with embodiment 2, and experimentation is: get 100 parts of latex and add in the cohesion still, under 35 ℃ of condensation temperatures, add 12 parts of disproportionated rosin soaps, and 10 part 20% sulfuric acid, 10 part 25% sodium-chlor fully mixes; Be warmed up to 60 ℃, slaking 5 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.The result is as follows: powder diameter 0.30mm～1.80mm, powder formation rate 79%, ash content 0.20%, fugitive constituent 0.25%, tens of seconds of swelling time, dissolution time 3 hours, stripping strength 60N/cm.
Embodiment 3
1. the modification of starch: in reaction flask, add 200 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 30 ℃, the dropping mass percentage concentration is 40% sodium hydroxide lye, make the pH value be elevated to 12, drip again mass percentage concentration and be 80% oxalic acid, make the pH value drop to 7, alkali lye and oxalic acid alternately drip, until 25 parts oxalic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 40min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 100 parts of water, 80 parts of solid contents are 40% polychloroprene latex, add successively 5 parts of isoprene, 15 portions of treated starches, 0.6 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.6 part of Potassium Persulphate when the polymeric kettle temperature reaches 25 ℃ and 5 parts of rosined soaps carry out graft polymerization reaction at 30 ℃.When polymerisation conversion is 65%, add 3 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 35 ℃ of condensation temperatures, add 8 parts of disproportionated rosin soaps, 10 part 20% sulfuric acid, 10 part 25% sodium-chlor fully mixes; Be warmed up to 40 ℃, slaking 7 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.Adopt classical way specimen structure and performance, the result is as follows: powder diameter 0.50mm～0.90mm, powder formation rate 99.5%, ash content 0.07%, fugitive constituent 0.12%, swelling time several seconds, dissolution time 1.5 hours, stripping strength 87N/cm.
Comparative Examples 3
Experiment condition does not just add isoprene with embodiment 3.Experimentation is: the 1. modification of starch: in reaction flask, add 200 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 30 ℃, the dropping mass percentage concentration is 40% sodium hydroxide lye, make the pH value be elevated to 12, drip again mass percentage concentration and be 80% oxalic acid, make the pH value drop to 7, alkali lye and oxalic acid alternately drip, until 25 parts oxalic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 40min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 100 parts of water, 80 parts of solid contents are 40% polychloroprene latex, add successively 15 portions of treated starches, 0.6 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.6 part of Potassium Persulphate when the polymeric kettle temperature reaches 25 ℃ and 5 parts of rosined soaps carry out graft polymerization reaction at 30 ℃.When polymerisation conversion is 65%, add 3 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 35 ℃ of condensation temperatures, add 8 parts of disproportionated rosin soaps, 10 part 20% sulfuric acid, 10 part 25% sodium-chlor fully mixes; Be warmed up to 40 ℃, slaking 7 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.The result is as follows: powder diameter 0.40mm～1.80mm, powder formation rate 70%, ash content 0.26%, fugitive constituent 0.28%, tens of seconds of swelling time, dissolution time 3.5 hours, stripping strength 63N/cm.
Embodiment 4
1. the modification of starch: in reaction flask, add 100 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 35 ℃, the dropping mass percentage concentration is 25% trolamine alkali lye, make the pH value be elevated to 10, drip again mass percentage concentration and be 90% oxalic acid, make the pH value drop to 7, alkali lye and oxalic acid alternately drip, until 30 parts oxalic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 60min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 100 parts of water, 100 parts of solid contents are 35% polychloroprene latex, add successively 10 parts of isoprene, 12 portions of treated starches, 0.5 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.5 part of Potassium Persulphate when the polymeric kettle temperature reaches 20 ℃ and 3 parts of rosined soaps carry out graft polymerization reaction at 40 ℃.When polymerisation conversion is 70%, add 5 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 25 ℃ of condensation temperatures, add 10 parts of disproportionated rosin soaps, 8 part 15% sulfuric acid, 8 part 15% sodium-chlor fully mixes; Be warmed up to 50 ℃, slaking 6 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.Adopt classical way specimen structure and performance, the result is as follows: powder diameter 0.40mm～0.90mm, powder formation rate 99.8%, ash content 0.09%, fugitive constituent 0.15%, swelling time several seconds, dissolution time 1.5 hours, stripping strength 90N/cm.
Comparative Examples 4
Experiment condition does not just add isoprene with embodiment 4.Experimentation is: the 1. modification of starch: in reaction flask, add 100 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 35 ℃, the dropping mass percentage concentration is 25% trolamine alkali lye, make the pH value be elevated to 10, drip again mass percentage concentration and be 90% oxalic acid, make the pH value drop to 7, alkali lye and oxalic acid alternately drip, until 30 parts oxalic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 60min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 100 parts of water, 100 parts of solid contents are 35% polychloroprene latex, add successively 12 portions of treated starches, 0.5 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.5 part of Potassium Persulphate when the polymeric kettle temperature reaches 20 ℃ and 3 parts of rosined soaps carry out graft polymerization reaction at 40 ℃.When polymerisation conversion is 70%, add 5 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 25 ℃ of condensation temperatures, add 10 parts of disproportionated rosin soaps, 8 part 15% sulfuric acid, 8 part 15% sodium-chlor fully mixes; Be warmed up to 50 ℃, slaking 6 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.The result is as follows: powder diameter 0.30mm～1.50mm, powder formation rate 70%, ash content 0.18%, fugitive constituent 0.25%, tens of seconds of swelling time, dissolution time 3 hours, stripping strength 65N/cm.
Embodiment 5
1. the modification of starch: in reaction flask, add 150 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 25 ℃, the dropping mass percentage concentration is 35% trolamine alkali lye, make the pH value be elevated to 11, drip again mass percentage concentration and be 65% oxalic acid, make the pH value drop to 7, alkali lye and oxalic acid alternately drip, until 15 parts oxalic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 70min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 90 parts of water, 100 parts of solid contents are 25% polychloroprene latex, add successively 20 parts of isoprene, 15 portions of treated starches, 1.2 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.8 part of Potassium Persulphate when the polymeric kettle temperature reaches 15 ℃ and 8 parts of rosined soaps carry out graft polymerization reaction at 35 ℃.When polymerisation conversion is 70%, add 5 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 25 ℃ of condensation temperatures, add 12 parts of disproportionated rosin soaps, 15 part 20% sulfuric acid, 10 part 30% sodium-chlor fully mixes; Be warmed up to 50 ℃, slaking 5 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.Adopt classical way specimen structure and performance, the result is as follows: powder diameter 0.40mm～0.80mm, powder formation rate 99.6%, ash content 0.05%, fugitive constituent 0.10%, swelling time several seconds, dissolution time 1.3 hours, stripping strength 88N/cm.
Comparative Examples 5
Do not add treated starch.Experiment is latex grafting isoprene and agglomeration process, condition is with embodiment 5, experimentation is: 1. add 90 parts of water in the 10L polymeric kettle, 100 parts of solid contents are 25% polychloroprene latex, add successively 20 parts of isoprene, 1.2 parts of sulphur are behind nitrogen replacement, stirring, heating treat to add 0.8 part of Potassium Persulphate when the polymeric kettle temperature reaches 15 ℃ and 8 parts of rosined soaps carry out graft polymerization reaction at 35 ℃.When polymerisation conversion is 70%, add 5 parts of phthalic acid dibutyl esters, make graft latex.2. get 100 parts of graft latexes and add in the cohesion still, under 25 ℃ of condensation temperatures, add 12 parts of disproportionated rosin soaps, 15 part 20% sulfuric acid, 10 part 30% sodium-chlor fully mixes; Be warmed up to 50 ℃, slaking 5 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.The result is as follows: powder diameter 0.30mm～1.80mm, powder formation rate 90%, ash content 0.17%, fugitive constituent 0.20%, several tens seconds of swelling time, dissolution time 4.5 hours, stripping strength 65N/cm.
Embodiment 6
1. the modification of starch: in reaction flask, add 500 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 35 ℃, drip mass percentage concentration and be 20% sodium hydroxide and the compound alkali lye of trolamine (sodium hydroxide and trolamine mass ratio 2: 1), make the pH value be elevated to 11, drip again mass percentage concentration and be 70% oxalic acid, make the pH value drop to 7, alkali lye and oxalic acid alternately drip, until 20 parts oxalic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 60min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 50 parts of water, 100 parts of solid contents are 40% polychloroprene latex, add successively 15 parts of isoprene, 20 portions of treated starches, 1.4 part sulphur, behind nitrogen replacement, stirring, heating treat to add 1.0 parts of Potassium Persulphates when the polymeric kettle temperature reaches 25 ℃ and 10 parts of rosined soaps carry out graft polymerization reaction at 45 ℃.When polymerisation conversion is 75%, add 10 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 30 ℃ of condensation temperatures, add 10 parts of disproportionated rosin soaps, 10 part 20% sulfuric acid, 10 part 30% sodium-chlor fully mixes; Be warmed up to 40 ℃, slaking 6 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.Adopt classical way specimen structure and performance, the result is as follows: powder diameter 0.40mm～0.90mm, powder formation rate 99.5%, ash content 0.09%, fugitive constituent 0.11%, swelling time several seconds, dissolution time 1.4 hours, stripping strength 88N/cm.
Comparative Examples 6
Do not add treated starch.Experiment is latex grafting isoprene and agglomeration process, condition is with embodiment 6, experimentation is: 1. add 50 parts of water in the 10L polymeric kettle, 100 parts of solid contents are 40% polychloroprene latex, add successively 15 parts of isoprene, 1.4 parts of sulphur are behind nitrogen replacement, stirring, heating treat to add 1.0 parts of Potassium Persulphates when the polymeric kettle temperature reaches 25 ℃ and 10 parts of rosined soaps carry out graft polymerization reaction at 45 ℃.When polymerisation conversion is 75%, add 10 parts of phthalic acid dibutyl esters, make graft latex.2. get 100 parts of graft latexes and add in the cohesion still, under 30 ℃ of condensation temperatures, add 10 parts of disproportionated rosin soaps, 10 part 20% sulfuric acid, 10 part 30% sodium-chlor fully mixes; Be warmed up to 40 ℃, slaking 6 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.The result is as follows: powder diameter 0.60mm～1.80mm, powder formation rate 92%, ash content 0.20%, fugitive constituent 0.15%, several tens seconds of swelling time, dissolution time 3.5 hours, stripping strength 75N/cm.
Embodiment 7
1. the modification of starch: in reaction flask, add 300 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 25 ℃, drip mass percentage concentration and be 30% sodium hydroxide and the compound alkali lye of trolamine (sodium hydroxide and trolamine mass ratio 2: 1), make the pH value be elevated to 12, drip again mass percentage concentration and be 80% carbonic acid, make the pH value drop to 7, alkali lye and carbonic acid alternately drip, until 25 parts carbonic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 50min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 160 parts of water, 100 parts of solid contents are 25% polychloroprene latex, add successively 20 parts of isoprene, 20 portions of treated starches, 0.5 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.5 part of Potassium Persulphate when the polymeric kettle temperature reaches 25 ℃ and 6 parts of rosined soaps carry out graft polymerization reaction at 40 ℃.When polymerisation conversion is 70%, add 5 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 25 ℃ of condensation temperatures, add 15 parts of disproportionated rosin soaps, 15 part 15% sulfuric acid, 5 part 15% sodium-chlor fully mixes; Be warmed up to 40 ℃, slaking 6 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.Adopt classical way specimen structure and performance, the result is as follows: powder diameter 0.40mm～0.90mm, powder formation rate 99.5%, ash content 0.10%, fugitive constituent 0.12%, swelling time several seconds, dissolution time 1.5 hours, stripping strength 92N/cm.
Comparative Examples 7
Not with starch conversion.Experiment is latex grafting isoprene, starch and agglomeration process, condition is with embodiment 7, experimentation is: 1. add 160 parts of water in the 10L polymeric kettle, 100 parts of solid contents are 25% polychloroprene latex, add successively 20 parts of isoprene, 20 parts of starch, 0.5 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.5 part of Potassium Persulphate when the polymeric kettle temperature reaches 25 ℃ and 6 parts of rosined soaps carry out graft polymerization reaction at 40 ℃.When polymerisation conversion is 70%, add 5 parts of phthalic acid dibutyl esters, make graft latex.2. get 100 parts of graft latexes and add in the cohesion still, under 25 ℃ of condensation temperatures, add 15 parts of disproportionated rosin soaps, 15 part 15% sulfuric acid, 5 part 15% sodium-chlor fully mixes; Be warmed up to 40 ℃, slaking 6 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.The result is as follows: powder diameter 1.0mm～3.50mm, powder formation rate 90%, ash content 0.40%, fugitive constituent 0.25%, tens of seconds of swelling time, dissolution time 3 hours, stripping strength 85N/cm.
Embodiment 8
1. the modification of starch: in reaction flask, add 100 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 35 ℃, the dropping mass percentage concentration is 40% sodium hydroxide lye, make the pH value be elevated to 11, drip again mass percentage concentration and be 90% oxalic acid, make the pH value drop to 7, alkali lye and oxalic acid alternately drip, until 30 parts oxalic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 40min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 120 parts of water, 100 parts of solid contents are 35% polychloroprene latex, add successively 15 parts of isoprene, 15 portions of treated starches, 1.0 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.8 part of Potassium Persulphate when the polymeric kettle temperature reaches 15 ℃ and 5 parts of rosined soaps carry out graft polymerization reaction at 40 ℃.When polymerisation conversion is 70%, add 10 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 35 ℃ of condensation temperatures, add 10 parts of disproportionated rosin soaps, 10 part 20% sulfuric acid, 10 part 25% sodium-chlor fully mixes; Be warmed up to 60 ℃, slaking 5 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.Adopt classical way specimen structure and performance, the result is as follows: powder diameter 0.40mm～0.90mm, powder formation rate 99.5%, ash content 0.08%, fugitive constituent 0.14%, swelling time several seconds, dissolution time 1.5 hours, stripping strength 90N/cm.
Comparative Examples 8
Not with starch conversion.Experiment is latex grafting isoprene, starch and agglomeration process, condition is with embodiment 8, experimentation is: 1. add 120 parts of water in the 10L polymeric kettle, 100 parts of solid contents are 35% polychloroprene latex, add successively 15 parts of isoprene, 15 parts of starch, 1.0 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.8 part of Potassium Persulphate when the polymeric kettle temperature reaches 15 ℃ and 5 parts of rosined soaps carry out graft polymerization reaction at 40 ℃.When the system transformation efficiency is 70%, add 10 parts of phthalic acid dibutyl esters, make graft latex.2. get 100 parts of graft latexes and add in the cohesion still, under 35 ℃ of condensation temperatures, add 10 parts of disproportionated rosin soaps, 10 part 20% sulfuric acid, 10 part 25% sodium-chlor fully mixes; Be warmed up to 60 ℃, slaking 5 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.The result is as follows: powder diameter 1.5mm～5.0mm, powder formation rate 95%, ash content 0.25%, fugitive constituent 0.20%, tens of seconds of swelling time, dissolution time 3.5 hours, stripping strength 85N/cm.
Embodiment 9
1. the modification of starch: in reaction flask, add 300 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 30 ℃, drip mass percentage concentration and be 20% sodium hydroxide and the compound alkali lye of trolamine (sodium hydroxide and trolamine mass ratio 2: 1), making the pH value is 10, drips mass percentage concentration again and be 80% carbonic acid, make the pH value drop to 7, alkali lye and carbonic acid alternately drip, until 20 parts carbonic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 60min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 60 parts of water, 100 parts of solid contents are 36% polychloroprene latex, add successively 8 parts of isoprene, 6 portions of treated starches, 0.8 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.7 part of Potassium Persulphate when the polymeric kettle temperature reaches 20 ℃ and 6 parts of rosined soaps carry out graft polymerization reaction at 45 ℃.When polymerisation conversion is 68%, add 5 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, under 35 ℃ of condensation temperatures, add 11 parts of disproportionated rosin soaps, 11 part 25% sulfuric acid, 15 part 25% sodium-chlor fully mixes; Be warmed up to 30 ℃, slaking 8 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.Adopt classical way specimen structure and performance, the result is as follows: powder diameter 0.40mm～0.70mm, powder formation rate 99.7%, ash content 0.07%, fugitive constituent 0.10%, swelling time several seconds, dissolution time 1.4 hours, stripping strength 95N/cm.
Comparative Examples 9
Experiment condition does not just prepare powder-product with graft latex with embodiment 9.Experimentation is: the 1. modification of starch: in reaction flask, add 300 parts of water, 100 parts of starch, stir, heat, maintain the temperature at 30 ℃, drip the alkali lye of mass percentage concentration 20%, making pH is 10, adds the carbonic acid of mass percentage concentration 80% again, makes pH drop to 7, alkali lye and carbonic acid alternately drip, until 20 parts carbonic acid adds, when treating that the variation of pH value is slow, regulating the pH value is 7, insulation 60min, the cooling blowing made treated starch after reaction finished.2. in the 10L polymeric kettle, add 60 parts of water, 100 parts of solid contents are 36% polychloroprene latex, add successively 8 parts of isoprene, 6 portions of treated starches, 0.8 part sulphur, behind nitrogen replacement, stirring, heating treat to add 0.7 part of Potassium Persulphate when the polymeric kettle temperature reaches 20 ℃ and 6 parts of rosined soaps carry out graft polymerization reaction at 45 ℃.When polymerisation conversion is 68%, add 5 parts of phthalic acid dibutyl esters, make graft latex.3. get 100 parts of graft latexes and add in the cohesion still, add 11 part 25% sulfuric acid under 35 ℃ of condensation temperatures, 15 part 25% sodium-chlor fully mixes; Be warmed up to 30 ℃, slaking 8 hours, separation, dehydration, drying make the powdered polychloroprene rubber product.Take directly to be condensed into block glue.The result is as follows: ash content 0.11%, fugitive constituent 0.20%, swelling time 4 hours, dissolution time 8 hours, stripping strength 75N/cm.
Claims (10)
1. the preparation method of a powdered polychloroprene rubber is characterized in that may further comprise the steps:
1) modification of starch: take starch as 100 mass parts, in reaction flask, add 60～500 parts of water and 100 parts of starch, stir, heat, temperature of reaction is controlled at 25～40 ℃, drips alkali lye, makes reacting liquid pH value be elevated to 10～12, dripping diprotic acid makes the pH value drop to 7 again, alkali lye and diprotic acid alternately drip, until diprotic acid drips fully, the add-on of diprotic acid is 15～30 parts, when the variation of question response liquid pH value is slow, add alkali lye, regulating the pH value is 7～8 again, insulation 40～70min, then the blowing of lowering the temperature makes treated starch;
2) preparation of graft latex: take polychloroprene latex as 100 mass parts, in polymeric kettle, add successively 100 parts of solid contents and be 25%～40% polychloroprene latex, 50～160 parts of water, 5～20 portions of treated starches, 5～20 parts of isoprene, 0.2～1.4 parts of molecular weight regulators, behind nitrogen replacement, stir, heat, treat to add 0.2～1.2 part of initiator and 3～10 parts of activators when the polymeric kettle temperature reaches 15～25 ℃, carry out graft polymerization reaction at 25～50 ℃, when polymerisation conversion reaches 65%～75%, add 2～10 parts of terminators, make graft latex;
3) condensation powdering: get 100 parts of graft latexes and add the cohesion still, under 10～30 ℃ of condensation temperatures, add 4～16 portions of separants, 4～16 parts of flocculation agents, 4～16 parts of flocculation agent, fully mix, be warming up to 20～60 ℃ of slakings 4～6 hours, then make speed through separation, dehydration, drying and separate molten high bonding environment-friendly type powdered polychloroprene rubber.
2. preparation method as claimed in claim 1 is characterized in that described starch is yam starch, sweet potato starch, tapioca (flour), W-Gum, wheat starch, green starch.
3. preparation method as claimed in claim 1 is characterized in that temperature of reaction is controlled at 30～35 ℃ in the described starch conversion process.
4. preparation method as claimed in claim 1 is characterized in that described diprotic acid is oxalic acid.
5. preparation method as claimed in claim 1, the add-on that it is characterized in that described diprotic acid is 15～20 parts.
6. preparation method as claimed in claim 1 is characterized in that the alkali lye that starch conversion is used is sodium hydroxide and trolamine complex liquid.
7. preparation method as claimed in claim 1 is characterized in that the treated starch consumption is 10～15 parts in the graft latex preparation process.
8. preparation method as claimed in claim 1 is characterized in that the isoprene consumption is 10～15 parts in the graft latex preparation process.
9. preparation method as claimed in claim 1 is characterized in that molecular weight regulator is sulphur or conditioning agent fourth in the graft latex preparation process, and add-on is 0.6～1.0 part.
10. preparation method as claimed in claim 1 is characterized in that polymerization temperature is 30～40 ℃ in the graft latex preparation process.
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| EP3087141A4 (en) * | 2013-12-23 | 2017-09-27 | Arlanxeo Singapore Pte. Ltd. | Highly pure halogenated rubbers |
| US10385200B2 (en) | 2014-06-30 | 2019-08-20 | Arlanxeo Singapore Pte. Ltd. | Anti-agglomerants for the rubber industry |
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| EP3087141A4 (en) * | 2013-12-23 | 2017-09-27 | Arlanxeo Singapore Pte. Ltd. | Highly pure halogenated rubbers |
| RU2699539C2 (en) * | 2013-12-23 | 2019-09-06 | Арланксео Сингапур Пте. Лтд. | Highly pure halogenated rubber |
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| US11584815B2 (en) | 2013-12-23 | 2023-02-21 | Arlanxeo Singapore Pte. Ltd. | Sealant comprising a polymeric composition including a lower critical solution temperature compound |
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| CN105733156A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method for xanthan gum-lignin powder chloroprene rubber |
| CN115703952A (en) * | 2021-08-16 | 2023-02-17 | 广西至善新材料科技有限公司 | Maleic acid single-corn starch ester modified nitrile-butadiene rubber adhesive and preparation method thereof |
| CN113583316A (en) * | 2021-08-27 | 2021-11-02 | 刘辉 | Waterproof and anti-pollution rubber material and preparation method thereof |
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