CN101240050A - Method for preparing crosslinked starch modifying cinepazid emulsion - Google Patents
Method for preparing crosslinked starch modifying cinepazid emulsion Download PDFInfo
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- CN101240050A CN101240050A CNA2008100196064A CN200810019606A CN101240050A CN 101240050 A CN101240050 A CN 101240050A CN A2008100196064 A CNA2008100196064 A CN A2008100196064A CN 200810019606 A CN200810019606 A CN 200810019606A CN 101240050 A CN101240050 A CN 101240050A
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Abstract
The invention relates to a modification for styrene acrylic emulsion, which including adding Composite emulsifier which is 1.0-15.5% by weight of all monomer into a four-mouth bottle equipped with agitator, reflux condenser pipe, thermometer and charging device, deionizing and emulsifying for 10min-3h, charging seed monomer and oxidized starch which is 1-50% by weight of all monomer under strong stirring to prepare transparent microemulsion of seed, heating slowly to 40-110 DEG C., charging initiator to initiate emulsion polymerization, adding surplus monomer drop by drop after emulsion being blue for 10min-4h, keeping temperature between 60-110 DEG C. for 30min-6h, regulate pH value to 6.5-10.5 with alkaline materials, continuously stirring for another 15min, then stopping heating, cooling. Then translucent styrene acrylic polymer emulsion modified by oxidized starch with content of solid material between 5% and 65% is obtained. The invention uses oxidized starch to modify styrene acrylic emulsion, enhances solid content of the emulsion, reduces content of free monomer, prolongs storage period, and reduces environmental pollution.
Description
Technical field
The present invention relates to the modification technology of preparing of a kind of benzene (ethene) third (olefin(e) acid) emulsion, especially a kind of preparation method who adopts crosslinked starch modifying cinepazid emulsion.Character such as described modifying cinepazid emulsion has shelf-stable, residual monomer content is low, bond strength good, with low cost.
Background technology
The styrene-acrylic resin emulsion is widely used a kind of Flock Adhesive stick in the textile industry of present China, in recent years, people are increasing to the demand of this type of environmental-protection type adhesive, although and commercially available styrene-acrylic resin tackiness agent is at raw material sources, product performance and quality stability aspect have suitable advantage and are widely used, but in actual use, still exist some problems, mainly contain: one, contain unreacted free monomer completely in the resin, influence the result of use of finished product, simultaneously environment is caused to a certain degree pollution, seriously endanger the healthy of people; Two, along with the anxiety of petroleum resources supply, as the petroleum chemicals of benzene emulsion adhesive raw materials, the supply of vinylformic acid and esters monomer thereof also is restricted gradually, makes the cost of this type of adhesive products constantly increase.Up to the present, textile industry sticks with glue the research direction of agent still with the master that is modified as to Emulsion acrylic resin, reduce free monomer content, improve the water tolerance of tackiness agent, and obtained certain effect, but still can not thoroughly solve a series of problems that residual monomer content and product cost rise steadily and bring.The strict day by day and health of people consciousness enhancing day by day along with environmental regulation, many developed countries are all developing and are developing solventless adhesives such as water system and hot-melting type energetically, producing and using low-cost environmental type tackiness agent then is trend of the times, so exploitation does not contain peculiar smell and green tackiness agent with low cost has active operation significance.
China's tackiness agent, 2004,13 (6): it is host with polyvinyl alcohol, treated starch, benzene emulsion that 8-10 has introduced a kind of, vulcabond is as the preparation method and the applied research of the environment-friendly type composite adhesive of linking agent, the result shows that the bonding strength of this composite adhesive is big, water-fast, resistance toheat good, but will bring certain problem of environmental pollution as polyvinyl alcohol, vulcabond etc. in the raw material that uses, and makes the application of this product be subjected to a certain degree restriction.
Summary of the invention
At the problems referred to above, the invention provides a kind of modification method for preparing of crosslinking-oxidization starch conversion styrene-acrylic resin emulsion.Because the C in the crosslinking-oxidization starch structure in the part glucose unit
6Last hydroxyl is converted into aldehyde radical, and aldehyde radical can form hemiacetal and acetal with hydroxyl and the carboxyl in the styrene-acrylic resin under heating condition, have the Sumstar 190 chain and participate in crosslinked three dimensional structure thereby when solidifying, form, and under condition of cure, can form acetal between the hydroformylation starch molecule and crosslinked.Because ethylidene ether structure has water-fast, alkaline-resisting, antioxidant, thereby has improved bonding strength and the water tolerance and the ageing-resistant performance of styrene-acrylic resin glue.After the simultaneous oxidation cross-linking starch adds the styrene-acrylic resin emulsion, thereby reduced the free monomer content in the resin, increased storage period, reduced environmental pollution because the hydroxyl that contains in its structure can form acetal with free acrylic ester monomer.
Preparation method of the present invention is:
Take into account compound emulsifying agent (negatively charged ion and nonionic emulsifying agent mass ratio are 0.1: 1.0～11.0: 1.0) and the deionized water emulsification 10min～3h that adds total monomer quality 1.0～15.5% in the four-hole bottle of feeding device in that agitator, reflux condensing tube, temperature are housed, powerfully stir adding seed monomer down (account for total monomer vinylbenzene and acrylate mass percent 1%～50%) and the Sumstar 190 of total monomer content 1～50% is made into transparent seed microemulsion.Slowly be warmed up to 40～100 ℃, add the initiator initiating polymerization of microemulsion by means, treat slowly to drip residual monomer after emulsion is blue light, drip off in 40min～4h, at 60～110 ℃ of insulation 30min～6h,, continue to stop heating behind the stirring 15min then with between alkaline matter regulation system pH value to 6.5～10.5, cooling discharging obtains total solid content and is 5～65% translucent oxidization starch modified cinepazid polymer emulsion.
The preparation of oxidization starch modified cinepazid polymer emulsion among the present invention, can obtain by the single stage method that Sumstar 190 and seed monomer add synchronously, also can in insulating process, add the crosslinked method of fractional steps of Sumstar 190 again and realize by preparing cinepazid polymer emulsion earlier.The solid content of resulting oxidization starch modified cinepazid polymer emulsion can be 5～65%, is preferably 25～50%.
The present invention is in the preparation process of oxidization starch modified cinepazid polymer emulsion, and used Sumstar 190 can be a hydrogen peroxide oxidation starch, and perchloric acid oxidation's starch also can be potassium permanganate oxidation starch, preferably hydrogen peroxide oxidation starch.Its consumption can be 1～50% of phenylpropyl alcohol total monomer content, preferably 5～20%.
The present invention is in the preparation process of oxidization starch modified cinepazid polymer emulsion, and acrylic ester monomer can be vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate etc., preferably butyl acrylate.The mass ratio of vinylbenzene and acrylate can be 10: 1～0.1: 1, is preferably 2.5: 1～1.0: 1.Seed monomer consumption can account for 1～50% of total monomer quality per-cent, and preferably 5～15%.
The present invention is in the preparation process of oxidization starch modified cinepazid polymer emulsion, and anionic emulsifier can be phosphoric acid ester (POS) in the used compound emulsifying agent, sodium lauryl sulphate (K
12), sodium laurylsulfonate (SDS), sulfated castor oil (ROS) etc., preferably SDS; Nonionic emulsifying agent can be lipid acid sorbyl alcohol (Span), polysorbate (Tween), alkylphenol polyoxyethylene (OP-10), preferably OP-10.Wherein negatively charged ion and nonionic emulsifying agent mass ratio are 0.1: 1.0～11.0: 1.0, preferably 0.4: 1.0～5.0: 1.0.Compound emulsifying agent accounts for total monomer quality 1.0～15.5%, and preferably 5.5～8.5%.
The present invention is in the preparation process of oxidization starch modified cinepazid polymer emulsion, and used initiator can be an ammonium persulphate, Potassium Persulphate, and hydrogen peroxide can also be Diisopropyl azodicarboxylate, preferably Potassium Persulphate.Its consumption can be monomeric 0.1～10% for accounting for, and preferably 1.0～4.5%.
The present invention is in the preparation process of oxidization starch modified cinepazid polymer emulsion, and the emulsification times of emulsifying agent in deionized water can be 10min～3h, preferably 30min～1h.The time of monomer dropping can be 40min～4h, preferably 1～1.5 hour.Dropping temperature can be preferably in 75～92 ℃ between 40～100 ℃.After dripping end, holding temperature can be 60～110 ℃, preferably 85～92 ℃.Soaking time can be 30min～6h, preferably 1～1.5h.
The present invention is in the preparation process of oxidization starch modified cinepazid polymer emulsion, and being used for regulating the finished product, to be weakly alkaline alkaline matter can be sodium hydroxide, sodium bicarbonate, and ammonium chloride, ammoniacal liquor also can be bicarbonate of ammonia, preferably sodium hydroxide.Its consumption is 0.005～0.2% of a total monomer content, preferably 0.01～0.05%.Regulation system is weakly alkaline pH value and can be preferably between 7.9～9.8 between 6.5～10.5.
The present invention uses the benefit of oxidization starch modified benzene emulsion, is that it has improved the solid content in the benzene emulsion, has reduced cost, both crosslinking reactions have been increased simultaneously, thereby reduced the free monomer content in the emulsion, increased storage period, reduced environmental pollution.Prepared product has good stability when room temperature, and high solids content makes it have advantages such as energy-conservation.
Embodiment: the present invention is described in detail below in conjunction with example, but the present invention is not limited to following example.
Embodiment 1
Take into account and add 0.04g anionic emulsifier K in the 1000mL four-hole bottle of feeding device in that agitator, reflux condensing tube, temperature are housed
12, 0.4g nonionic emulsifying agent Span and 853g deionized water emulsification 10min, the powerful stirring adds 0.4g vinylbenzene and 0.04 vinylformic acid down and is made into transparent seed microemulsion as seed monomer and perchloric acid oxidation's starch 0.44g.Slowly be warmed up to 40 ℃, add 0.04g ammonium persulphate initiating polymerization of microemulsion by means, treat slowly to drip remaining 39.6g vinylbenzene and 3.96g vinylformic acid after emulsion is blue light, drip off in the 4h, at 60 ℃ of insulation 6h,, continue to stop heating behind the stirring 15min then with 0.00055g sodium hydroxide regulation system pH value to 6.5, cooling discharging obtains solid content and is 5% translucent oxidization starch modified cinepazid polymer emulsion SBT-1.
Embodiment 2
Take into account and add 6g anionic emulsifier SDS, 2g nonionic emulsifying agent Tween and 192g deionized water emulsification 1h in the 500mL four-hole bottle of feeding device in that agitator, reflux condensing tube, temperature are housed, the powerful stirring adds 9g vinylbenzene and 6g methyl methacrylate down and is made into transparent seed microemulsion as seed monomer and potassium permanganate oxidation starch 8g.Slowly be warmed up to 82 ℃, add 1.8g Potassium Persulphate initiating polymerization of microemulsion by means, treat slowly to drip remaining 51g vinylbenzene and 34g methyl methacrylate after emulsion is blue light, drip off in the 2h, at 92 ℃ of insulation 1.5h,, continue to stop heating behind the stirring 15min then with 3g bicarbonate of ammonia regulation system pH value to 8.9, cooling discharging obtains solid content and is 38% translucent oxidization starch modified cinepazid polymer emulsion SBT-2.
Embodiment 3
Take into account and add 6g anionic emulsifier SDS, 3g nonionic emulsifying agent OP-10 and 331g deionized water emulsification 30min in the 1000mL four-hole bottle of feeding device in that agitator, reflux condensing tube, temperature are housed, the powerful stirring adds 10g vinylbenzene and 5g butyl acrylate down and is made into transparent seed microemulsion as seed monomer and hydrogen peroxide oxidation starch 15g.Slowly be warmed up to 75 ℃, add 4.5g Potassium Persulphate initiating polymerization of microemulsion by means, treat slowly to drip remaining 90g vinylbenzene and 45g butyl acrylate after emulsion is blue light, 1.5h in drip off, at 88 ℃ of insulation 1h,, continue to stop heating behind the stirring 15min then with 0.03g ammoniacal liquor regulation system pH value to 9.5, cooling discharging obtains solid content and is 35% translucent oxidization starch modified cinepazid polymer emulsion SBT-3.
Embodiment 4
Take into account and add 5.5g anionic emulsifier ROS, 0.5g nonionic emulsifying agent Span and 150g deionized water emulsification 30min in the 500mL four-hole bottle of feeding device in that agitator, reflux condensing tube, temperature are housed, the powerful stirring adds 2.5g vinylbenzene and 2.5g methacrylic acid down and is made into transparent seed microemulsion as the seed monomer.Slowly be warmed up to 78 ℃, add 4g hydrogen peroxide initiating polymerization of microemulsion by means, treat slowly to drip remaining 47.5g vinylbenzene and 47.5g methacrylic acid after emulsion is blue light, 1.5h in drip off the back and add potassium permanganate oxidation starch 18g, at 90 ℃ of insulation 45min,, continue to stop heating behind the stirring 15min then with 0.006g ammoniacal liquor regulation system pH value to 7.0, cooling discharging obtains solid content and is 46% translucent oxidization starch modified cinepazid polymer emulsion SBT-4.
Embodiment 5
Take into account and add 7.28g anionic emulsifier phosphoric acid ester, 1.82g nonionic emulsifying agent OP-10 and 66g deionized water emulsification 45min in the 250mL four-hole bottle of feeding device in that agitator, reflux condensing tube, temperature are housed, the powerful stirring adds 10g vinylbenzene and 4g ethyl propenoate down and is made into transparent seed microemulsion as seed monomer and potassium permanganate oxidation starch 21g.Slowly be warmed up to 70 ℃, add 3.5g hydrogen peroxide initiating polymerization of microemulsion by means, treat slowly to drip remaining 40g vinylbenzene and 16g ethyl propenoate after emulsion is blue light, 2.5h in drip off, at 98 ℃ of insulation 45min,, continue to stop heating behind the stirring 15min then with 0.0063g ammonium chloride regulation system pH value to 7.5, cooling discharging obtains solid content and is 61% translucent oxidization starch modified cinepazid polymer emulsion SBT-5.
Embodiment 6
Take into account and add 5.68g anionic emulsifier POS, 1.14g nonionic emulsifying agent Tween and 33.8g deionized water emulsification 3h in the 250mL four-hole bottle of feeding device in that agitator, reflux condensing tube, temperature are housed, the powerful stirring adds 2g vinylbenzene and 20g methyl acrylate down and is made into transparent seed microemulsion as seed monomer and potassium permanganate oxidation starch 22g.Slowly be warmed up to 100 ℃, add 4.4g Diisopropyl azodicarboxylate initiating polymerization of microemulsion by means, treat slowly to drip remaining 2g vinylbenzene and 20g methyl acrylate after emulsion is blue light, drip off in the 40min, at 110 ℃ of insulation 30min,, continue to stop heating behind the stirring 15min then with 0.08g sodium bicarbonate regulation system pH value to 10.5, cooling discharging obtains solid content and is 65% translucent oxidization starch modified cinepazid polymer emulsion SBT-6.
Embodiment 7
Take into account and add 3.6g anionic emulsifier ROS, 2.4g nonionic emulsifying agent Span and 150g deionized water emulsification 40min in the 500mL four-hole bottle of feeding device in that agitator, reflux condensing tube, temperature are housed, the powerful stirring adds 2.5g vinylbenzene and 2.5g butyl acrylate down and is made into transparent seed microemulsion as the seed monomer.Slowly be warmed up to 78 ℃, add 4g hydrogen peroxide initiating polymerization of microemulsion by means, treat slowly to drip remaining 47.5g vinylbenzene and 47.5g butyl acrylate after emulsion is blue light, 1.5h in drip off, at 90 ℃ of insulation 45min,, continue to stop heating behind the stirring 15min then with 0.008g ammoniacal liquor regulation system pH value to 7.0, cooling discharging, obtaining solid content is 42% translucent unmodified cinepazid polymer emulsion BT.
Experimental technique
Measure the particle diameter and the viscosity of the oxidization starch modified cinepazid polymer emulsion sample of part, the result is as shown in following table 1.
The partial properties index of table 1 cinepazid polymer emulsion sample
| Sample | Sumstar 190 accounts for the mass percent (%) of styrene-acrylic polymer | Free monomer content (%) | Storage period (moon) |
| BT | 0 | 1.15 | ＞12 |
| SBT-1 SBT-2 SBT-3 SBT-4 SBT-5 SBT-6 | 1.0 8.0 10.0 18.0 30.0 50.0 | 0.63 0.32 0.30 0.21 0.18 0.11 | ＞10 ＞10 ＞10 ＞8 ＞6 ＞6 |
The result shows that the oxidization starch modified cinepazid polymer emulsion of product of the present invention has package stability preferably when the Sumstar 190 consumption is little.The adding of Sumstar 190 has significantly reduced the free monomer content in the emulsion, has reduced environmental pollution.The preparation technology of this tackiness agent is simple, and equipment requirements is low, adopts crosslinking-oxidization starch as properties-correcting agent, sufficient raw, low price sticks with glue field such as agent at weaving, leather and has better development prospect, thereby has favorable economic benefit and social benefit.Be that the problem of environmental pollution that tackiness agent causes has positive social effect to solving traditional styrene-acrylic resin emulsion simultaneously.
Claims (8)
1. the preparation method of crosslinked starch modifying cinepazid emulsion, it is characterized in that agitator is being housed, reflux condensing tube, temperature is taken into account negatively charged ion that adds total monomer quality 1.0～15.5% in the four-hole bottle of feeding device and compound emulsifying agent and the deionized water emulsification 10min～3h that the nonionic emulsifying agent mass ratio is 0.1: 1.0～11.0: 1.0, the powerful stirring adds 1%～50% the seed monomer that accounts for total monomer vinylbenzene and acrylate mass percent down and the Sumstar 190 of total monomer content 1～50% is made into transparent seed microemulsion, slowly be warmed up to 40～100 ℃, add the initiator initiating polymerization of microemulsion by means, treat slowly to drip residual monomer after emulsion is blue light, drip off in 40min～4h, at 60～110 ℃ of insulation 30min～6h, then with between alkaline matter regulation system pH value to 6.5～10.5, stop heating after continuing to stir 15min, cooling discharging obtains total solid content and is 5～65% translucent oxidization starch modified cinepazid polymer emulsion.
2. the preparation method of crosslinked starch modifying cinepazid emulsion according to claim 1, it is characterized in that obtaining by the single stage method that Sumstar 190 and seed monomer add synchronously, or by preparing cinepazid polymer emulsion earlier, in insulating process, add the crosslinked method of fractional steps of Sumstar 190 again and realize that the solid content of resulting oxidization starch modified cinepazid polymer emulsion is 5～65%.
3. the preparation method of crosslinked starch modifying cinepazid emulsion according to claim 1, it is characterized in that used Sumstar 190 is a hydrogen peroxide oxidation starch, perchloric acid oxidation's starch, or potassium permanganate oxidation starch, hydrogen peroxide oxidation starch preferably, its consumption is 1～50% of a phenylpropyl alcohol total monomer content, or 5～20%.
4. the preparation method of crosslinked starch modifying cinepazid emulsion according to claim 1 is characterized in that acrylic ester monomer is vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, vinylformic acid fourth or be preferably 2.5: 1～1.0: 1; Seed monomer consumption accounts for 1～50% of total monomer quality per-cent, or is 5～15%.
5. the preparation method of crosslinked starch modifying cinepazid emulsion according to claim 1, anionic emulsifier can be to be phosphoric acid ester POS, sodium lauryl sulphate K in the used compound emulsifying agent of its feature
12, sodium laurylsulfonate SDS, sulfated castor oil ROS, or SDS; Nonionic emulsifying agent is lipid acid sorbyl alcohol Span, polysorbate Tween, alkylphenol polyoxyethylene OP-10, or OP-10; Wherein negatively charged ion and nonionic emulsifying agent mass ratio are 0.1: 1.0～11.0: 1.0, or 0.4: 1.0～5.0: 1.0, compound emulsifying agent accounts for total monomer quality 1.0～15.5%, or 5.5～8.5%.
6. the preparation method of crosslinked starch modifying cinepazid emulsion according to claim 1, the used initiator of its feature is an ammonium persulphate, Potassium Persulphate, hydrogen peroxide, or Diisopropyl azodicarboxylate, or Potassium Persulphate; Its consumption can be monomeric 0.1～10% for accounting for, or 1.0～4.5%.
7. the preparation method of crosslinked starch modifying cinepazid emulsion according to claim 1, the emulsification times of its feature emulsifying agent in deionized water is 10min～3h, or 30min～1h.The time of monomer dropping is 40min～4h, or 1～1.5 hour.Dropping temperature is between 40～100 ℃, or at 75～92 ℃; After dripping end, holding temperature is 60～110 ℃, or 85～92 ℃; Soaking time is 30min～6h, or 1～1.5h.
8. the preparation method of crosslinked starch modifying cinepazid emulsion according to claim 1, its feature is used for regulating the finished product, and to be weakly alkaline alkaline matter be sodium hydroxide, sodium bicarbonate, ammonium chloride, ammoniacal liquor, or bicarbonate of ammonia, or sodium hydroxide, its consumption is 0.005～0.2% of a total monomer content, or 0.01～0.05%, and regulation system is weakly alkaline pH value or between 7.9～9.8.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102268232A (en) * | 2010-06-07 | 2011-12-07 | 上海伟佳家具有限公司 | Aldehyde-free adhesive and purpose thereof |
| CN102977258A (en) * | 2012-12-28 | 2013-03-20 | 上海东升新材料有限公司 | Styrene acrylic latex for surface coating as well as preparation method and application thereof |
| CN103614101A (en) * | 2013-11-15 | 2014-03-05 | 刘方 | Formaldehyde-free adhesive and application method thereof |
| CN105924583A (en) * | 2016-06-30 | 2016-09-07 | 浙江弘利防渗胶有限公司 | Preparation method of colorless nano surface sizing agent |
| CN112343901A (en) * | 2020-11-27 | 2021-02-09 | 安徽银禾木业有限公司 | Solid wood furniture board connecting piece |
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- 2008-03-10 CN CNA2008100196064A patent/CN101240050A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268232A (en) * | 2010-06-07 | 2011-12-07 | 上海伟佳家具有限公司 | Aldehyde-free adhesive and purpose thereof |
| CN102268232B (en) * | 2010-06-07 | 2013-02-20 | 上海伟佳家具有限公司 | Aldehyde-free adhesive and purpose thereof |
| CN102977258A (en) * | 2012-12-28 | 2013-03-20 | 上海东升新材料有限公司 | Styrene acrylic latex for surface coating as well as preparation method and application thereof |
| CN103614101A (en) * | 2013-11-15 | 2014-03-05 | 刘方 | Formaldehyde-free adhesive and application method thereof |
| CN105924583A (en) * | 2016-06-30 | 2016-09-07 | 浙江弘利防渗胶有限公司 | Preparation method of colorless nano surface sizing agent |
| CN112343901A (en) * | 2020-11-27 | 2021-02-09 | 安徽银禾木业有限公司 | Solid wood furniture board connecting piece |
| CN112343901B (en) * | 2020-11-27 | 2022-03-22 | 安徽银禾木业有限公司 | Solid wood furniture board connecting piece |
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Open date: 20080813 |