CN102952303B - 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
Binding type chloroprene rubber is the important source material of tackiness agent industry.Because its excellent performance, its Application Areas are 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.Binding type powdered polychloroprene rubber, compared with traditional sheet glue, has the advantages such as energy-saving and cost-reducing, to improve production process 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: n) be (C6H10O5) to be formed by connecting through sugared key by many dehydrated glucose units, on C2, the C3 of each glucose unit and C5, respectively there is a hydroxyl, thereby just have thousands of activity hydroxies on a starch chain high-polymer molecular, and each starch granules is interweaved and forms with the form in crystallizing field and unsetting district by unnumbered amylose starch and amylopectin molecular chain.To powder neoprene, not only improve the adhesive property of sizing agent by starch-grafted, and improved dissolution rate, broadened application scope, more environmental protection.
Starch is carried out gelatinization by CN03100424.5, 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.Qi Qing etc. (" research of Starch/SBR Composites structure and performance ", rubber industry, 2007,54 volumes, 4 phases, 197-202) adopt phenolic resin modified starch, and then treated starch and styrene-butadiene latex blend are condensed altogether.Zhang Jing etc. are at " application of environmental protection starch adhesive on timber " (Heilongjiang Vocational Institute of Ecological Engineering's journal, 2009,22 volumes, 1 phase, 53-55), introduced grafting modified of starch adhesive for wood and starch esterification/copolymerization adhesive for wood, conventional graft copolymerization reagent 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, 6 phases, 13-16) make W-Gum and diprotic acid generation part esterification, add stablizer water soluble polymer, make starch adhesive host.When impregnation, add industrial flour, solid content is reached more than 45%, then add 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 manufacture the research of API sizing agent ", Beihua University's journal (natural science edition), 2004,5 volumes, 4 phases, 361-364) by diprotic acid and W-Gum generation part esterification, under the condition of stablizer polyoxyethylene glycol existence, add carboxy nitrile rubber latex and esterification W-Gum mixing copolymerization, make starch adhesive host.Add POV barium as filler, polyisocyanate compound, as linking agent, adds the encapsulant of hydrosulphite as temporary transient blocked isocyanate group simultaneously, effectively extends the working life of sizing agent.The timber-work such as glued board, core-board of its mongolicum Turcz. with Modified Starch Adhesive compacting all reaches 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 the tackiness agent that obtains a kind of high adhesion, available epoxy, vinyl acetate fat, urea, phenolic aldehyde, polyester, butyronitrile product rubber, silicon rubber, starch, protein and natural rubber etc. are as the main body of tackiness agent, make the nuclei of crystallization with zinc oxide.In a kind of rubber combination that JP2009073981 introduces, contain the components such as rubber, polysaccharide and carbon black.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: taking 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 DEG C, drips alkali lye, makes reacting liquid pH value be raised to 10~12, dripping diprotic acid makes pH value drop to 7 again, alkali lye and diprotic acid alternately drip, until diprotic acid drips completely, 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 pH value is 7~8 again, insulation 40~70min, then the blowing of lowering the temperature, makes treated starch;
2) preparation of graft latex: taking polychloroprene latex as 100 mass parts, in polymeric kettle, add successively the polychloroprene latex that 100 parts of solid contents are 25%~40%, 50~160 parts of water, 5~20 portions of treated starches, 5~20 parts of isoprene, 0.2~1.4 part of molecular weight regulator, with after nitrogen replacement, stir, heat, in the time that polymeric kettle temperature reaches 15~25 DEG C, add 0.2~1.2 part of initiator and 3~10 parts of activators, carry out graft polymerization reaction at 25~50 DEG C, in the time that 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 cohesion still, under 10~30 DEG C of condensation temperatures, add 4~16 portions of separants, 4~16 parts of flocculation agents, 4~16 parts of flocculation agent, fully be uniformly mixed, be warming up to 20~60 DEG C of slakings 4~6 hours, then separate molten high bonding environment-friendly type powdered polychloroprene rubber through separation, dehydration, the dry speed that makes.
In the present invention, starch is various starch, as yam starch, sweet potato starch, tapioca (flour), W-Gum, wheat starch, green starch, and preferably W-Gum.
Because amidin is being stirred into after cream while leaving standstill, have starch and slowly precipitate, be the stability problem that solves starch water-in-oil emulsion, and further improve its binding property, the present invention need to carry out modification to starch.In starch conversion process, the consumption of water is 60~500 parts, and starch water miscible liquid concentration is 20%~60%, 200~300 parts of preferably water consumptions.
In the present invention, starch conversion temperature is controlled at 25~40 DEG C, preferably 30~35 DEG C.
The acid that in the present invention, starch conversion is used is diprotic acid, as oxalic acid, carbonic acid etc., and preferably oxalic acid, mass percentage concentration is 60%~90%, is preferably 70%~80%.Diprotic acid add-on deficiency, the esterification of W-Gum is also not enough, and has precipitation to form; And diprotic acid add-on is too much, starch excessive degradation, long easily generation storage period starch suspension liquid gelatin phenomenon, in the present invention, the add-on of diprotic acid is 15~30 parts, preferably 15~20 parts.
The alkali lye that in the present invention, starch conversion is used is alkali or alkali salt or its complex liquid, and as sodium hydroxide, trolamine, potassium hydroxide etc. and complex liquid thereof, alkali lye mass percentage concentration is 20%~40%, preferably 25%~35%.Preferably sodium hydroxide and trolamine complex liquid.
In the present invention, starch conversion alkali lye and diprotic acid alternately drip, and add alkali lye to make pH be raised to 10~12, then add diprotic acid to make pH drop to 7, until diprotic acid drips completely.When reaction has been tending towards, pH value changes slowly, then adds alkali lye, and regulating pH value is 7~8.
In the present invention, starch conversion has reacted rear insulation 40~70min, the blowing of then lowering the temperature.
In the preparation process of graft latex of the present invention, in order to ensure 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 controlling graft latex is 25%~35%.
In the preparation process of graft latex, treated starch consumption is 5~20 parts, preferably 10~15 parts; Isoprene consumption is 5~20 parts, preferably 10~15 parts.
The molecular weight regulator adopting in the preparation process of graft latex is sulphur or conditioning agent fourth, is 0.2~1.4 part, preferably 0.6~1.0 part; The initiator adopting both can use water-soluble inorganic peroxide thermolysis type initiator, also can use the oxidation-reduction initiator being formed by water-soluble inorganic peroxide and reductive agent, for making the powder-product that crystal property is good, the oxidation-reduction initiator preferably being 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.
In the present invention, activator is selected from rosined soap, petroleum sodium sulfonate, formaldehyde-naphthalene 5 sulfonic acid condenses sodium salts, and preferably rosined soap, is 3~10 parts.
In the present invention, graft latex polymerization temperature is 25~50 DEG C, preferably 30~40 DEG C.
In the present invention, graft polymerization conversion rate control is 65%~75%, for reducing gel content, and preferably 65%~70%.
In the present invention, terminator is selected phthalic acid dibutyl ester, and consumption is 2~10 parts.
The present invention, taking soap as separant, is selected from disproportionated rosin soap, fatty acid soaps etc., preferably disproportionated rosin soap, and consumption is 4~16 parts, preferably 5~10 parts.
In the present invention, taking mineral acid as flocculation agent, be selected from sulfuric acid, hydrochloric acid etc., preferably sulfuric acid, consumption is 4~16 parts, preferably 5~10 parts.
In the present invention, taking mineral acid sodium salt as flocculation agent, be selected from sodium sulfate, sodium-chlor etc., preferably sodium-chlor, mass concentration is 15%~20%, every 100 parts of graft latex consumptions are 4~20 parts, preferably 5~10 parts.
In the present invention, in condensation powdering process, powder particle curing temperature is 20~60 DEG C, and preferably 40~50 DEG C, 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, tool has the following advantages:
(1) starch and polychloroprene latex, isoprene generation graft crosslinking, has improved solvability and the cohesive force of sizing agent.Starch both, as a part for sizing agent, had and strengthened the property latex again, made sizing agent have higher clinging power and water tolerance.
(2) starch source is abundant, has the advantages such as quality is light, corrosion-free, pollution-free, 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, makes in product nonrubber component content lower, and performance is better.
(4) when the powdered rubber that prepared by the present invention uses as sizing agent, there is the part advantage of starch adhesive, strengthened the advantage of neoprene sizing agent, expanded range of application.
(5) treated starch and isoprene generation graft polymerization, make isoprene more easily be condensed into trans isoprene, and the kindliness of trans isoprene molecular chain makes the easier condensation powdering of graft latex.
(6) interaction of treated starch and isoprene, makes sizing agent concentrate advantage separately, and performance is more good.
(7) the powdered polychloroprene rubber particle diameter that prepared by the present invention is even, be 0.4~0.8mm, and the powder formation rate of graft latex can reach more than 99.5%.
(8) the powdered polychloroprene rubber several seconds that adopts the inventive method to prepare is swellable, within 2 hours, can dissolve completely, more than stripping strength can reach 90N/cm.And swollen need of sheet peptization 3~5 hours, within 6~12 hours, (needing to stir) just can complete dissolving.
Embodiment
Below by specific embodiment, the preparation method of binding type powdered polychloroprene rubber of the present invention is described in further detail.
Polychloroprene latex: domestic polychloroprene latex CR244, total solid content is 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 DEG C, to drip mass percentage concentration be 20% sodium hydroxide and the compound alkali lye of trolamine (sodium hydroxide and trolamine mass ratio are 1: 1), makes pH value be elevated to 10, then to drip mass percentage concentration be 60% oxalic acid, make pH value drop to 7, alkali lye and oxalic acid alternately drip, until the oxalic acid of 15 parts adds, in the time that the variation of pH value is slow, regulating pH value is 8, insulation 50min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 100 parts of water, 100 parts of polychloroprene latexs that solid content is 35%, add successively 10 parts of isoprene, 12 portions of treated starches, 0.5 part of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 25 DEG C, polymeric kettle temperature add 0.5 part of Potassium Persulphate and 3 parts of rosined soaps to carry out graft polymerization reaction at 40 DEG C.In the time that 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 cohesion still, under 25 DEG C of condensation temperatures, add 10 parts of disproportionated rosin soaps, the sulfuric acid of 8 part 15%, the sodium-chlor of 8 part 15%, is fully uniformly mixed; Be warmed up to 50 DEG C, slaking 6 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Adopt classical way test sample structure and performance, 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 example 1
Do not add isoprene and treated starch, test as cohesion experiment, condition is with embodiment 1, experimentation is: get 100 parts of latex and add in cohesion still, add 10 parts of disproportionated rosin soaps, the sulfuric acid of 8 part 15% under 25 DEG C of condensation temperatures, the sodium-chlor of 8 part 15%, is fully uniformly mixed; Be warmed up to 50 DEG C, slaking 6 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.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 DEG C, to drip mass percentage concentration be 30% sodium hydroxide and the compound alkali lye of trolamine (sodium hydroxide and trolamine mass ratio 1: 2), makes pH value be elevated to 11, then to drip mass percentage concentration be 70% oxalic acid, make pH value drop to 7, alkali lye and oxalic acid alternately drip, until the oxalic acid of 20 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 60min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 100 parts of water, 100 parts of polychloroprene latexs that solid content is 30%, add successively 20 parts of isoprene, 10 portions of treated starches, 0.6 part of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 15 DEG C, polymeric kettle temperature add 0.9 part of Potassium Persulphate and 4 parts of rosined soaps to carry out graft polymerization reaction at 35 DEG C.In the time that 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 cohesion still, under 35 DEG C of condensation temperatures, add 12 parts of disproportionated rosin soaps, the sulfuric acid of 10 part 20%, the sodium-chlor of 10 part 25%, is fully uniformly mixed; Be warmed up to 60 DEG C, slaking 5 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Adopt classical way test sample structure and performance, 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 example 2
Do not add isoprene and treated starch.Experiment is cohesion experiment, and condition is with embodiment 2, and experimentation is: get 100 parts of latex and add in cohesion still, under 35 DEG C of condensation temperatures, add 12 parts of disproportionated rosin soaps, and the sulfuric acid of 10 part 20%, the sodium-chlor of 10 part 25%, is fully uniformly mixed; Be warmed up to 60 DEG C, slaking 5 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.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 DEG C, the sodium hydroxide lye that dropping mass percentage concentration is 40%, make pH value be elevated to 12, then to drip mass percentage concentration be 80% oxalic acid, make pH value drop to 7, alkali lye and oxalic acid alternately drip, until the oxalic acid of 25 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 40min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 100 parts of water, 80 parts of polychloroprene latexs that solid content is 40%, add successively 5 parts of isoprene, 15 portions of treated starches, 0.6 part of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 25 DEG C, polymeric kettle temperature add 0.6 part of Potassium Persulphate and 5 parts of rosined soaps to carry out graft polymerization reaction at 30 DEG C.In the time that 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 cohesion still, under 35 DEG C of condensation temperatures, add 8 parts of disproportionated rosin soaps, the sulfuric acid of 10 part 20%, the sodium-chlor of 10 part 25%, is fully uniformly mixed; Be warmed up to 40 DEG C, slaking 7 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Adopt classical way test sample structure and performance, 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 example 3
Experiment condition, with embodiment 3, does not just add isoprene.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 DEG C, the sodium hydroxide lye that dropping mass percentage concentration is 40%, make pH value be elevated to 12, then to drip mass percentage concentration be 80% oxalic acid, make pH value drop to 7, alkali lye and oxalic acid alternately drip, until the oxalic acid of 25 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 40min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 100 parts of water, 80 parts of polychloroprene latexs that solid content is 40%, add successively 15 portions of treated starches, 0.6 part of sulphur, with after nitrogen replacement, stir, heat, in the time that polymeric kettle temperature reaches 25 DEG C, add 0.6 part of Potassium Persulphate and 5 parts of rosined soaps to carry out graft polymerization reaction at 30 DEG C.In the time that 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 cohesion still, under 35 DEG C of condensation temperatures, add 8 parts of disproportionated rosin soaps, the sulfuric acid of 10 part 20%, the sodium-chlor of 10 part 25%, is fully uniformly mixed; Be warmed up to 40 DEG C, slaking 7 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.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 DEG C, the trolamine alkali lye that dropping mass percentage concentration is 25%, make pH value be elevated to 10, then to drip mass percentage concentration be 90% oxalic acid, make pH value drop to 7, alkali lye and oxalic acid alternately drip, until the oxalic acid of 30 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 60min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 100 parts of water, 100 parts of polychloroprene latexs that solid content is 35%, add successively 10 parts of isoprene, 12 portions of treated starches, 0.5 part of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 20 DEG C, polymeric kettle temperature add 0.5 part of Potassium Persulphate and 3 parts of rosined soaps to carry out graft polymerization reaction at 40 DEG C.In the time that 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 cohesion still, under 25 DEG C of condensation temperatures, add 10 parts of disproportionated rosin soaps, the sulfuric acid of 8 part 15%, the sodium-chlor of 8 part 15%, is fully uniformly mixed; Be warmed up to 50 DEG C, slaking 6 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Adopt classical way test sample structure and performance, 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 example 4
Experiment condition, with embodiment 4, does not just add isoprene.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 DEG C, the trolamine alkali lye that dropping mass percentage concentration is 25%, make pH value be elevated to 10, then to drip mass percentage concentration be 90% oxalic acid, make pH value drop to 7, alkali lye and oxalic acid alternately drip, until the oxalic acid of 30 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 60min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 100 parts of water, 100 parts of polychloroprene latexs that solid content is 35%, add successively 12 portions of treated starches, 0.5 part of sulphur, with after nitrogen replacement, stir, heat, in the time that polymeric kettle temperature reaches 20 DEG C, add 0.5 part of Potassium Persulphate and 3 parts of rosined soaps to carry out graft polymerization reaction at 40 DEG C.In the time that 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 cohesion still, under 25 DEG C of condensation temperatures, add 10 parts of disproportionated rosin soaps, the sulfuric acid of 8 part 15%, the sodium-chlor of 8 part 15%, is fully uniformly mixed; Be warmed up to 50 DEG C, slaking 6 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.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 DEG C, the trolamine alkali lye that dropping mass percentage concentration is 35%, make pH value be elevated to 11, then to drip mass percentage concentration be 65% oxalic acid, make pH value drop to 7, alkali lye and oxalic acid alternately drip, until the oxalic acid of 15 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 70min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 90 parts of water, 100 parts of polychloroprene latexs that solid content is 25%, add successively 20 parts of isoprene, 15 portions of treated starches, 1.2 parts of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 15 DEG C, polymeric kettle temperature add 0.8 part of Potassium Persulphate and 8 parts of rosined soaps to carry out graft polymerization reaction at 35 DEG C.In the time that 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 cohesion still, under 25 DEG C of condensation temperatures, add 12 parts of disproportionated rosin soaps, the sulfuric acid of 15 part 20%, the sodium-chlor of 10 part 30%, is fully uniformly mixed; Be warmed up to 50 DEG C, slaking 5 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Adopt classical way test sample structure and performance, 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 example 5
Do not add treated starch.Experiment is latex grafting isoprene and agglomeration process, condition is with embodiment 5, experimentation is: 1. in 10L polymeric kettle, add 90 parts of water, 100 parts of polychloroprene latexs that solid content is 25%, add successively 20 parts of isoprene, 1.2 parts of sulphur, with after nitrogen replacement, stir, heat, in the time that polymeric kettle temperature reaches 15 DEG C, add 0.8 part of Potassium Persulphate and 8 parts of rosined soaps to carry out graft polymerization reaction at 35 DEG C.In the time that 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 cohesion still, under 25 DEG C of condensation temperatures, add 12 parts of disproportionated rosin soaps, the sulfuric acid of 15 part 20%, the sodium-chlor of 10 part 30%, is fully uniformly mixed; Be warmed up to 50 DEG C, slaking 5 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Result is as follows: powder diameter 0.30mm~1.80mm, powder formation rate 90%, ash content 0.17%, fugitive constituent 0.20%, swelling time number tens seconds, 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 DEG C, to drip mass percentage concentration be 20% sodium hydroxide and the compound alkali lye of trolamine (sodium hydroxide and trolamine mass ratio 2: 1), makes pH value be elevated to 11, then to drip mass percentage concentration be 70% oxalic acid, make pH value drop to 7, alkali lye and oxalic acid alternately drip, until the oxalic acid of 20 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 60min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 50 parts of water, 100 parts of polychloroprene latexs that solid content is 40%, add successively 15 parts of isoprene, 20 portions of treated starches, 1.4 parts of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 25 DEG C, polymeric kettle temperature add 1.0 parts of Potassium Persulphates and 10 parts of rosined soaps to carry out graft polymerization reaction at 45 DEG C.In the time that 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 cohesion still, under 30 DEG C of condensation temperatures, add 10 parts of disproportionated rosin soaps, the sulfuric acid of 10 part 20%, the sodium-chlor of 10 part 30%, is fully uniformly mixed; Be warmed up to 40 DEG C, slaking 6 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Adopt classical way test sample structure and performance, 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 example 6
Do not add treated starch.Experiment is latex grafting isoprene and agglomeration process, condition is with embodiment 6, experimentation is: 1. in 10L polymeric kettle, add 50 parts of water, 100 parts of polychloroprene latexs that solid content is 40%, add successively 15 parts of isoprene, 1.4 parts of sulphur, with after nitrogen replacement, stir, heat, in the time that polymeric kettle temperature reaches 25 DEG C, add 1.0 parts of Potassium Persulphates and 10 parts of rosined soaps to carry out graft polymerization reaction at 45 DEG C.In the time that 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 cohesion still, under 30 DEG C of condensation temperatures, add 10 parts of disproportionated rosin soaps, the sulfuric acid of 10 part 20%, the sodium-chlor of 10 part 30%, is fully uniformly mixed; Be warmed up to 40 DEG C, slaking 6 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Result is as follows: powder diameter 0.60mm~1.80mm, powder formation rate 92%, ash content 0.20%, fugitive constituent 0.15%, swelling time number tens seconds, 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 DEG C, to drip mass percentage concentration be 30% sodium hydroxide and the compound alkali lye of trolamine (sodium hydroxide and trolamine mass ratio 2: 1), makes pH value be elevated to 12, then to drip mass percentage concentration be 80% carbonic acid, make pH value drop to 7, alkali lye and carbonic acid alternately drip, until the carbonic acid of 25 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 50min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 160 parts of water, 100 parts of polychloroprene latexs that solid content is 25%, add successively 20 parts of isoprene, 20 portions of treated starches, 0.5 part of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 25 DEG C, polymeric kettle temperature add 0.5 part of Potassium Persulphate and 6 parts of rosined soaps to carry out graft polymerization reaction at 40 DEG C.In the time that 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 cohesion still, under 25 DEG C of condensation temperatures, add 15 parts of disproportionated rosin soaps, the sulfuric acid of 15 part 15%, the sodium-chlor of 5 part 15%, is fully uniformly mixed; Be warmed up to 40 DEG C, slaking 6 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Adopt classical way test sample structure and performance, 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 example 7
Not by starch conversion.Experiment is latex grafting isoprene, starch and agglomeration process, condition is with embodiment 7, experimentation is: 1. in 10L polymeric kettle, add 160 parts of water, 100 parts of polychloroprene latexs that solid content is 25%, add 20 parts of isoprene successively, 20 parts of starch, 0.5 part of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 25 DEG C, polymeric kettle temperature add 0.5 part of Potassium Persulphate and 6 parts of rosined soaps to carry out graft polymerization reaction at 40 DEG C.In the time that 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 cohesion still, under 25 DEG C of condensation temperatures, add 15 parts of disproportionated rosin soaps, the sulfuric acid of 15 part 15%, the sodium-chlor of 5 part 15%, is fully uniformly mixed; Be warmed up to 40 DEG C, slaking 6 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.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 DEG C, the sodium hydroxide lye that dropping mass percentage concentration is 40%, make pH value be elevated to 11, then to drip mass percentage concentration be 90% oxalic acid, make pH value drop to 7, alkali lye and oxalic acid alternately drip, until the oxalic acid of 30 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 40min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 120 parts of water, 100 parts of polychloroprene latexs that solid content is 35%, add successively 15 parts of isoprene, 15 portions of treated starches, 1.0 parts of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 15 DEG C, polymeric kettle temperature add 0.8 part of Potassium Persulphate and 5 parts of rosined soaps to carry out graft polymerization reaction at 40 DEG C.In the time that 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 cohesion still, under 35 DEG C of condensation temperatures, add 10 parts of disproportionated rosin soaps, the sulfuric acid of 10 part 20%, the sodium-chlor of 10 part 25%, is fully uniformly mixed; Be warmed up to 60 DEG C, slaking 5 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Adopt classical way test sample structure and performance, 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 example 8
Not by starch conversion.Experiment is latex grafting isoprene, starch and agglomeration process, condition is with embodiment 8, experimentation is: 1. in 10L polymeric kettle, add 120 parts of water, 100 parts of polychloroprene latexs that solid content is 35%, add 15 parts of isoprene successively, 15 parts of starch, 1.0 parts of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 15 DEG C, polymeric kettle temperature add 0.8 part of Potassium Persulphate and 5 parts of rosined soaps to carry out graft polymerization reaction at 40 DEG C.In the time that 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 cohesion still, under 35 DEG C of condensation temperatures, add 10 parts of disproportionated rosin soaps, the sulfuric acid of 10 part 20%, the sodium-chlor of 10 part 25%, is fully uniformly mixed; Be warmed up to 60 DEG C, slaking 5 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.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 DEG C, to drip mass percentage concentration be 20% sodium hydroxide and the compound alkali lye of trolamine (sodium hydroxide and trolamine mass ratio 2: 1), making pH value is 10, then to drip mass percentage concentration be 80% carbonic acid, make pH value drop to 7, alkali lye and carbonic acid alternately drip, until the carbonic acid of 20 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 60min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 60 parts of water, 100 parts of polychloroprene latexs that solid content is 36%, add successively 8 parts of isoprene, 6 portions of treated starches, 0.8 part of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 20 DEG C, polymeric kettle temperature add 0.7 part of Potassium Persulphate and 6 parts of rosined soaps to carry out graft polymerization reaction at 45 DEG C.In the time that 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 cohesion still, under 35 DEG C of condensation temperatures, add 11 parts of disproportionated rosin soaps, the sulfuric acid of 11 part 25%, the sodium-chlor of 15 part 25%, is fully uniformly mixed; Be warmed up to 30 DEG C, slaking 8 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Adopt classical way test sample structure and performance, 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 example 9
Experiment condition, with embodiment 9, is not just prepared powder-product by graft latex.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 DEG C, drip the alkali lye of mass percentage concentration 20%, making pH is 10, then adds the carbonic acid of mass percentage concentration 80%, makes pH drop to 7, alkali lye and carbonic acid alternately drip, until the carbonic acid of 20 parts adds, in the time that the variation of pH value is slow, regulating pH value is 7, insulation 60min, reaction finishes rear cooling blowing, makes treated starch.2. in 10L polymeric kettle, add 60 parts of water, 100 parts of polychloroprene latexs that solid content is 36%, add successively 8 parts of isoprene, 6 portions of treated starches, 0.8 part of sulphur, with after nitrogen replacement, stir, heat, in the time that reaching 20 DEG C, polymeric kettle temperature add 0.7 part of Potassium Persulphate and 6 parts of rosined soaps to carry out graft polymerization reaction at 45 DEG C.In the time that 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 cohesion still, add the sulfuric acid of 11 part 25% under 35 DEG C of condensation temperatures, the sodium-chlor of 15 part 25%, is fully uniformly mixed; Be warmed up to 30 DEG C, slaking 8 hours, separation, dehydration, the dry powdered polychloroprene rubber product that makes.Take to be directly condensed into block glue.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. a preparation method for powdered polychloroprene rubber, is characterized in that comprising the following steps:
1) modification of starch: taking 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 DEG C, drips alkali lye, makes reacting liquid pH value be elevated to 10~12, dripping diprotic acid makes pH value drop to 7 again, alkali lye and diprotic acid alternately drip, until diprotic acid drips completely, 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 pH value is 7~8 again, insulation 40~70min, then the blowing of lowering the temperature, makes treated starch;
2) preparation of graft latex: taking polychloroprene latex as 100 mass parts, in polymeric kettle, add successively the polychloroprene latex that 100 parts of solid contents are 25%~40%, 50~160 parts of water, 5~20 portions of described treated starches, 5~20 parts of isoprene, 0.2~1.4 part of molecular weight regulator, with after nitrogen replacement, stir, heat, in the time that polymeric kettle temperature reaches 15~25 DEG C, add 0.2~1.2 part of initiator and 3~10 parts of activators, carry out graft polymerization reaction at 25~50 DEG C, in the time that polymerisation conversion reaches 65%~75%, add 2~10 parts of terminators, make graft latex;
3) condensation powdering: get 100 parts of described graft latexes and add cohesion still, under 10~30 DEG C of condensation temperatures, add 4~16 portions of separants, 4~16 parts of flocculation agents, 4~16 parts of flocculation agent, fully be uniformly mixed, be warming up to 20~60 DEG C of slakings 4~6 hours, then separate molten high bonding environment-friendly type powdered polychloroprene rubber through separation, dehydration, the dry speed that makes.
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 in described starch conversion process, temperature of reaction is controlled at 30~35 DEG C.
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, is characterized in that the add-on of 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 in graft latex preparation process, treated starch consumption is 10~15 parts.
8. preparation method as claimed in claim 1, is characterized in that in graft latex preparation process, isoprene consumption is 10~15 parts.
9. preparation method as claimed in claim 1, is characterized in that in graft latex preparation process, molecular weight regulator is sulphur or conditioning agent fourth, and add-on is 0.6~1.0 part.
10. preparation method as claimed in claim 1, is characterized in that in graft latex preparation process, polymerization temperature is 30~40 DEG C.
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SG11201610902QA (en) | 2014-06-30 | 2017-01-27 | Arlanxeo Singapore Pte Ltd | Novel anti-agglomerants for the rubber industry |
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 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3984361A (en) * | 1975-05-30 | 1976-10-05 | The United States Of America As Represented By The Secretary Of Agriculture | Preparation of graft polymer latexes by sonification |
CN1517393A (en) * | 2003-01-13 | 2004-08-04 | 北京化工大学 | Preparation method of starch and polymer comosition |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5883076A (en) * | 1981-11-10 | 1983-05-18 | Sugiyama Sangyo Kagaku Kenkyusho | Water-resistant adhesive |
-
2011
- 2011-08-19 CN CN201110240429.4A patent/CN102952303B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3984361A (en) * | 1975-05-30 | 1976-10-05 | The United States Of America As Represented By The Secretary Of Agriculture | Preparation of graft polymer latexes by sonification |
CN1517393A (en) * | 2003-01-13 | 2004-08-04 | 北京化工大学 | Preparation method of starch and polymer comosition |
Non-Patent Citations (9)
Title |
---|
JP昭58-83076A 1983.05.18 |
刘光远.利用玉米淀粉生产耐水性无臭胶粘剂的研究.《林产工业》.1999,第26卷(第6期),13-16. |
利用玉米淀粉生产耐水性无臭胶粘剂的研究;刘光远;《林产工业》;19991231;第26卷(第6期);13-16 * |
利用玉米淀粉的酯化制造API胶粘剂研究;时君友;《北华大学学报》;20040831;第5卷(第4期);361-367 * |
吕生华.降解淀粉与乙烯基类单体接枝聚合物的合成及应用.《精细化工》.2001,第18卷(第5期),281-283. |
时君友.利用玉米淀粉的酯化制造API胶粘剂研究.《北华大学学报》.2004,第5卷(第4期),361-367. |
粉末氯丁橡胶-244的制备及与块状氯丁橡胶的比较;魏绪玲;《合成橡胶工业》;20130315;第34卷(第2期);95-98 * |
降解淀粉与乙烯基类单体接枝聚合物的合成及应用;吕生华;《精细化工》;20010531;第18卷(第5期);281-283 * |
魏绪玲.粉末氯丁橡胶-244的制备及与块状氯丁橡胶的比较.《合成橡胶工业》.2013,第34卷(第2期),95-98. |
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