CN104004185A - Novel process for producing low-chloride polyamide epichlorohydrin resin - Google Patents
Novel process for producing low-chloride polyamide epichlorohydrin resin Download PDFInfo
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- CN104004185A CN104004185A CN201410254971.9A CN201410254971A CN104004185A CN 104004185 A CN104004185 A CN 104004185A CN 201410254971 A CN201410254971 A CN 201410254971A CN 104004185 A CN104004185 A CN 104004185A
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- epichlorohydrin resin
- low chlorine
- polyamine epichlorohydrin
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Abstract
The invention discloses a novel process for producing low-chloride polyamide epichlorohydrin resin. The process comprises the following steps: adding a certain amount of epichlorohydrin to a pre-polymer polyamide under an agitation condition, and controlling the reaction temperature at 55 DEG C or below; reacting for two hours or more, so as to prepare low-crosslinked and high-branched polyamide epichlorohydrin resin; continuing to heat to 60 DEG C or more, and preparing high-crosslinked and high-branched polyamide epichlorohydrin resin after the viscosity is increased to the preset viscosity; adjusting the pH to 2.0-7.0 to terminate by using an inorganic acid or an organic acid free of chlorine, so as to prepare the low chloride polyamide epichlorohydrin resin; adding different dilution water according to the requirements, and adjusting the product to different solid content. The low-chloride polyamide epichlorohydrin resin is prepared by adopting three steps, the side reaction condition of epichlorohydrin is inhibited, the conversion ratio of the epichlorohydrin is improved, the organic chloride content in the product is reduced, the production technology disclosed by the invention is simple and practical, and short in production cycle, and continuous production can be achieved.
Description
Technical field
The invention belongs to the technical field of superpolymer graft modification, relate to a kind of chloride cationoid properties-correcting agent polymeric amide is carried out to the new production process that low chlorine polyamine epichlorohydrin resin is prepared in modification.
Background technology
Polyamide polyamine epichlorhydrin resin (be called for short PPE) is wet strength agent for papermaking curing under neutrallty condition, has that whiteness highly, neutral is solidified, retention is high, an advantage such as release formaldehyde not, has market widely at paper industry.But at present use epoxy chloropropane as cation-modified reagent in production process, produce a large amount of organochlorine by products in production process, these muriates and fiber collection are not very firm, easily enter the waste water system in paper mill and produce chlorine-contained wastewater pollution; These organochlorine by products are adsorbable organochlorine simultaneously, can partly remain in paper product, have certain carinogenicity, and human consumer's health is impacted.Along with the raising of state health standards and environmental requirement, in product, the restriction of cl content will be more and more stricter.
Summary of the invention
The object of the invention is the content in order to reduce organochlorine in existing polyamide polyamine epichlorhydrin resin, proposed the novel process that a kind of three steps are prepared low chlorine polyamine epichlorohydrin resin.Taking epoxy chloropropane as modifying agent, to performed polymer polymeric amide carry out grafting, cross-linking modified after, stop with not chloride mineral acid or organic acid for adjusting pH value, then add as required dilution water to adjust different solid contents, preparation method is: 1. the temperature of the performed polymer polymeric amide of certain solid content is controlled to 55 DEG C or following, under agitation add quantitative epoxy chloropropane, react 2 hours or more than, make the branched polyamide epichlorohydrin resin of low cross-linking; 2. by the temperature increase to 60 of the branched polyamide epichlorohydrin resin of low cross-linking DEG C or more than, after viscosity reaches predetermined value, add a certain amount of acid to stop, pH value is adjusted to 2.0～7.0, make low chlorine polyamine epichlorohydrin resin; 3. according to different demands, low chlorine polyamine epichlorohydrin resin is diluted with water to 8%～30% solid content, and obtains product.The present invention adopts three steps to prepare low chlorine polyamine epichlorohydrin resin, has improved the transformation efficiency of epoxy chloropropane, has reduced the content of organochlorine in product; And production technique of the present invention is simple, with short production cycle, can be continuously produced.
Embodiment
Embodiment one: 1. take 100g solid content and be 50% performed polymer polymeric amide (amine content is 0.18mol), add dilution water 50g, under stirring state, in 30min, be added dropwise to epoxy chloropropane 19.98g(0.216mol), at 55 DEG C, react 3 hours, make the branched polyamide epichlorohydrin resin of low cross-linking.2. continue to be warmed up to 65 DEG C, rise to 55s(until viscosity and be coated with 4# cup detection numerical value) after, the acetic acid that is 5% by volumetric molar concentration is adjusted to 2.5 by pH value, makes the low chlorine polyamine epichlorohydrin resin of high solids content; 3. be diluted with water to solid content 12.5%, and must low chlorine polyamine epichlorohydrin resin.
Embodiment two: 1. take 100g solid content and be 50% performed polymer polymeric amide (amine content is 0.18mol), add dilution water 100g, under stirring state, in 20min, drip epoxy chloropropane 24.98g(0.26mol), at 50 DEG C, react 5 hours, make the branched polyamide epichlorohydrin resin of low cross-linking.2. continue to be warmed up to 70 DEG C, rise to 50s(until viscosity and be coated with 4# cup detection numerical value) after, the sulfuric acid that is 5% by volumetric molar concentration is adjusted to 3.5 by pH value, makes the low chlorine polyamine epichlorohydrin resin of high solids content; 3. be diluted with water to solid content 15%, and must low chlorine polyamine epichlorohydrin resin.
Embodiment three: 1. take 100g solid content and be 50% performed polymer polymeric amide (amine content is 0.18mol), add dilution water 100g, under stirring state, the disposable epoxy chloropropane 16.65g(0.18mol that adds), at 45 DEG C, react 6 hours, make the branched polyamide epichlorohydrin resin of low cross-linking.2. continue to be warmed up to 75 DEG C, rise to 45s(until viscosity and be coated with 4# cup detection numerical value) after, the acetic acid that is 5% by volumetric molar concentration is adjusted to 6.0 by pH value, makes the low chlorine polyamine epichlorohydrin resin of high solids content; 3. be diluted with water to solid content 20%, and must low chlorine polyamine epichlorohydrin resin.
Embodiment four: 1. take 100g solid content and be 50% performed polymer polymeric amide (amine content is 0.18mol), add dilution water 200g, under stirring state, the disposable epoxy chloropropane 26.65g(0.288mol that adds), at 55 DEG C, react 8 hours, make the branched polyamide epichlorohydrin resin of low cross-linking.2. continue to be warmed up to 80 DEG C, rise to 28s(until viscosity and be coated with 4# cup detection numerical value) after, the nitric acid that is 5% by volumetric molar concentration is adjusted to 4.5 by pH value, makes the low chlorine polyamine epichlorohydrin resin of high solids content; 3. be diluted with water to solid content 30%, and must low chlorine polyamine epichlorohydrin resin.
Claims (11)
1. a novel process of producing low chlorine polyamine epichlorohydrin resin, comprises the steps:
(1) the performed polymer polymeric amide of certain solid content is under agitation added to quantitative epoxy chloropropane, temperature is controlled at 55 DEG C or following, react 2 hours or more than, make the high branched polyamide epichlorohydrin resin of low cross-linking;
(2) by the temperature increase to 60 of high low cross-linking branched polyamide epichlorohydrin resin DEG C or more than, after viscosity reaches predetermined value, add certain density acid that pH value is adjusted to 2.0～7.0 and stop, make low chlorine polyamine epichlorohydrin resin;
(3), according to different demands, low chlorine polyamine epichlorohydrin resin is diluted with water to 8%～30% solid content, and obtains product.
2. the new production process of low chlorine polyamine epichlorohydrin resin according to claim 1, is characterized in that, the solid content of the performed polymer polymeric amide shown in step (1) is more than or equal to 20%.
3. the new production process of low chlorine polyamine epichlorohydrin resin according to claim 1, is characterized in that, the addition manner of the epoxy chloropropane shown in step (1) can disposablely add, and also can slowly add continuously or segmentation interpolation.
4. the new production process of low chlorine polyamine epichlorohydrin resin according to claim 1, is characterized in that, in the mole number of the epoxy chloropropane addition shown in step (1) and performed polymer polymeric amide, the ratio of imido grpup mole number is more than or equal to 0.8.
5. the new production process of low chlorine polyamine epichlorohydrin resin according to claim 1, is characterized in that, the temperature of reaction shown in step (1) is less than or equal to 55 DEG C.
6. the new production process of low chlorine polyamine epichlorohydrin resin according to claim 1, is characterized in that, the reaction times shown in step (1) is more than or equal to 2 hours.
7. the new production process of low chlorine polyamine epichlorohydrin resin according to claim 1, is characterized in that, the temperature of reaction of the high branched polyamide epichlorohydrin resin of low cross-linking shown in step (2) is more than or equal to 60 DEG C.
8. the new production process of low chlorine polyamine epichlorohydrin resin according to claim 1, is characterized in that, the predetermined viscosity shown in step (2) is at room temperature coated with 4# cup detection numerical value and is more than or equal to 12 seconds.
9. the new production process of low chlorine polyamine epichlorohydrin resin according to claim 1, is characterized in that, the termination acid shown in step (2) is not chloride mineral acid or organic acid; In termination acid, hydrogen ion concentration is less than or equal to 5mol/L.
10. the new production process of low chlorine polyamine epichlorohydrin resin according to claim 1, is characterized in that, the consumption of the termination acid shown in step (2) is that low chlorine polyamine epichlorohydrin resin pH value is adjusted to 2.0～7.0 consumption.
The new production process of 11. low chlorine polyamine epichlorohydrin resins according to claim 1, is characterized in that, the solid content of the low chlorine polyamine epichlorohydrin resin product shown in step (3) is 8%～30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410254971.9A CN104004185A (en) | 2014-06-11 | 2014-06-11 | Novel process for producing low-chloride polyamide epichlorohydrin resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410254971.9A CN104004185A (en) | 2014-06-11 | 2014-06-11 | Novel process for producing low-chloride polyamide epichlorohydrin resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112796158A (en) * | 2021-01-20 | 2021-05-14 | 上海东升新材料有限公司 | High-solid low-chlorine water repellent agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1548650A (en) * | 2003-05-08 | 2004-11-24 | 费会林 | Prepn process of epichlorohydrin wet strength agent for polyamide and polyamine |
| JP2009149732A (en) * | 2007-12-19 | 2009-07-09 | Kao Corp | Method for producing polyamideamine-epihalohydrin resin |
| CN102391619A (en) * | 2011-08-24 | 2012-03-28 | 广西大学 | Preparation method of permeation resistant addition agent with functions of reinforcing stiffness and wet-strength |
-
2014
- 2014-06-11 CN CN201410254971.9A patent/CN104004185A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1548650A (en) * | 2003-05-08 | 2004-11-24 | 费会林 | Prepn process of epichlorohydrin wet strength agent for polyamide and polyamine |
| JP2009149732A (en) * | 2007-12-19 | 2009-07-09 | Kao Corp | Method for producing polyamideamine-epihalohydrin resin |
| CN102391619A (en) * | 2011-08-24 | 2012-03-28 | 广西大学 | Preparation method of permeation resistant addition agent with functions of reinforcing stiffness and wet-strength |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112796158A (en) * | 2021-01-20 | 2021-05-14 | 上海东升新材料有限公司 | High-solid low-chlorine water repellent agent and preparation method thereof |
| CN112796158B (en) * | 2021-01-20 | 2022-12-09 | 上海东升新材料有限公司 | High-solid low-chlorine water repellent agent and preparation method thereof |
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Application publication date: 20140827 |