CN104140511B - For dry-spinning high solids content modified melamine-formaldehyde resin and preparation method - Google Patents
For dry-spinning high solids content modified melamine-formaldehyde resin and preparation method Download PDFInfo
- Publication number
- CN104140511B CN104140511B CN201410351095.1A CN201410351095A CN104140511B CN 104140511 B CN104140511 B CN 104140511B CN 201410351095 A CN201410351095 A CN 201410351095A CN 104140511 B CN104140511 B CN 104140511B
- Authority
- CN
- China
- Prior art keywords
- formaldehyde resin
- dry
- modified melamine
- formaldehyde
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention belongs to resin preparation field, be specially a kind of for dry-spinning high solids content modified melamine-formaldehyde resin and preparation method thereof.This modified melamine-formaldehyde resin comprises the raw material of following weight part: 10-100 part trimeric cyanamide, 15-600 part formaldehyde, 1-30 part properties-correcting agent, 1-30 part polymeric alcohol, 50-150 part de-salted water, 0.1-5 part pH adjusting agent, 0.1-10 part modified silicon oil, 0.1-10 part softening agent.The solid content of this modified melamine-formaldehyde resin is 60%-85%.The solid content of obtained terpolycyantoamino-formaldehyde resin is high, and degree of crosslinking is moderate, and storage process medium viscosity is stablized, and is applicable to dry-spinning; Owing to adding polymeric alcohol, introduce alcoholic extract hydroxyl group and add the water-soluble of terpolycyantoamino-formaldehyde resin and stability, add the distance between triazine ring simultaneously, make final obtained melamine fiber have higher elongation at break.
Description
Technical field
The invention belongs to resin preparation field, be specially a kind of for dry-spinning high solids content modified melamine-formaldehyde resin and preparation method thereof.
Background technology
Terpolycyantoamino-formaldehyde resin has higher reactivity and bridging property, is widely used in the industries such as wood working, moulding compound, wet strength agent, coating crosslinking agent, leather composite tanning agent, fabric finishing agent and uses.
Melamine formaldehyde fiber, also known as melamine fiber, without fusing point, not molten drop, be a kind of difficulty combustion, resistant to elevated temperatures high-performance special fiber, having been widely used, is the bright spot of trimeric cyanamide new opplication in recent years.Common terpolycyantoamino-formaldehyde resin solid content is below 55%, and molecular weight, degree of crosslinking is high, and along with the increase of solid content or molecular weight increase, the water-soluble and bad stability of resin, separates out, bleaches from water.Such melamino-formaldehyde formaldehyde resin is large through the melamine fiber fragility that spinning is obtained, and intensity is low, can not carry out post-treatment, substantially without using value.Patent CN100516325A " method processed of melamine formaldehyde resin/polyvinyl alcohol flame-proof fiber ", mixes obtained spinning solution the melamino-formaldehyde formaldehyde resin aqueous solution with polyvinyl alcohol water solution, then obtains fire-retardant fibre through wet-spinning.Patent CN1344821A " a kind of fire-retardant fibre and manufacture method thereof ", adds inorganic nano material in terpolycyantoamino-formaldehyde resin, then obtains fire-retardant fibre through centrifugal spinning.Patent CN100516325A introduces polyvinyl alcohol, improves spinning property, but polyvinyl alcohol reduces the flame retardant resistance of fiber, and the melamino-formaldehyde formaldehyde resin simultaneously mixed and polyvinyl alcohol water solution poor stability, be unfavorable for industrial production.There is agglomeration in the inorganic nano material that patent CN1344821A adds, there is the problem of spinning solution poor stability equally in terpolycyantoamino-formaldehyde resin.The domestic report that yet there are no melamine fiber industrial test or production.
Summary of the invention
In order to the molecular weight, the degree of crosslinking that solve above conventional terpolycyantoamino-formaldehyde resin existence are high, poor stability, be not suitable for the problem of spinning, the invention provides a kind of realize melamino-formaldehyde formaldehyde resin through spinning obtain melamine fiber for dry-spinning high solids content modified melamine-formaldehyde resin.
Another object of the present invention is to provide a kind of preparation method for dry-spinning high solids content modified melamine-formaldehyde resin.
Technical scheme of the present invention is:
A kind of for dry-spinning high solids content modified melamine-formaldehyde resin, this modified melamine-formaldehyde resin comprises the raw material of following weight part: 10-100 parts of trimeric cyanamides, 15-600 part formaldehyde, 1-30 parts of properties-correcting agent, 1-30 parts of polymeric alcohols, 50-150 parts of de-salted waters, 0.1-5 parts of pH adjusting agents, 0.1-10 parts of modified silicon oils, 0.1-10 parts of softening agent.The solid content of this modified melamine-formaldehyde resin is 60%-85%.
As preferably, for dry-spinning high solids content modified melamine-formaldehyde resin, this modified melamine-formaldehyde resin comprises the raw material of following weight part: 10-30 parts of trimeric cyanamides, 15-90 part formaldehyde, 2-10 parts of properties-correcting agent, 2-10 parts of polymeric alcohols, 10-35 parts of de-salted waters, 0.1-2 parts of pH adjusting agents, 0.1-3 parts of modified silicon oils, 0.1-2 parts of softening agent.
Described formaldehyde is formaldehyde solution or paraformaldehyde; Described polymeric alcohol be polyoxyethylene glycol series, polypropylene glycol is serial, polyvinyl alcohol is serial, PTMG serial in any one, such as Macrogol 200, polyvinyl alcohol 1799F.
Described properties-correcting agent is containing any one in the pyrrolotriazine derivatives of alkyl, aralkyl, terminal hydroxy group, such as benzoguanamine, first substituted melamine, hydroxyethyl trimeric cyanamide or hydroxyl ethoxyethyl trimeric cyanamide.Described pH adjusting agent is any one in inorganic alkaline thing or organic amine, as sodium hydroxide, potassium hydroxide, sodium carbonate, diethylamine, triethylamine or diethanolamine etc.
Described modified silicon oil is methyl-silicone oil, hydroxy silicon oil or polyether modified silicon oil etc.Described softening agent is any one in phosphoric acid ester, soap or fatty acid ester.Such as stearic acid, sodium stearate, tributyl phosphate etc.
The present invention, based on terpolycyantoamino-formaldehyde resin, introduces great amount of hydroxy group increase resin water-soluble, increases the stability of resin; Introduce soft segment, increase the distance between triazine ring, improve the elongation at break of final melamine fiber; Add properties-correcting agent, reduce the degree of crosslinking of terpolycyantoamino-formaldehyde resin, improve elongation at break and the snappiness of final melamine fiber.The melamine fiber performance obtained through the terpolycyantoamino-formaldehyde resin of modification improves greatly, and breaking tenacity, elongation at break, snappiness etc. all meet post-treatment requirement.
For a preparation method for dry-spinning high solids content modified melamine-formaldehyde resin, it comprises the following steps:
The first step: by raw material accurate measurement, adds efficient strong-mixing reactor;
Second step, in efficient strong-mixing reactor, under higher pH condition, reacts: 30-60 DEG C of pre-reactions 20 minutes-1 hour at twice; React 3-7 hours under 80-95 DEG C of conditions;
3rd step, fast cooling is cooled to 35-40 DEG C, and stopped reaction obtains modified melamine-formaldehyde resin;
4th step, by the resin that obtains in the 3rd step after filtration, bubble removal step, remove impurity and microbubble in resin;
5th step, resin transfer is to spinning process.
Described efficient strong-mixing reactor is multiaxis planet stirring reactor or screw reactor.The pH value of described higher pH condition is 8.5-12, and the conditional value of preferred pH is 10-11.5.The mol ratio of formaldehyde and trimeric cyanamide is 2-8:1
Compared with prior art, beneficial effect of the present invention is:
(1) solid content of terpolycyantoamino-formaldehyde resin that the present invention obtains reaches as high as 80%, and degree of crosslinking is moderate, and storage process medium viscosity is stablized, and is applicable to dry-spinning.Use this resin spinning, spinning process can continuous and steady operation more than 200 hours.
(2) add polymeric alcohol in the present invention's reaction, introduce alcoholic extract hydroxyl group and add the water-soluble of terpolycyantoamino-formaldehyde resin and stability, add the distance between triazine ring simultaneously, make final obtained melamine fiber have higher elongation at break.
(3) higher in the present invention's reaction pH value, effectively can promote to generate linear melamino-formaldehyde molecule, be conducive to the spinning property of terpolycyantoamino-formaldehyde resin.
(4) introduce pyrrolotriazine derivatives in the present invention's reaction, reduce the degree of crosslinking of terpolycyantoamino-formaldehyde resin, reduce the fragility of resin, add the spinning property of terpolycyantoamino-formaldehyde resin, make final obtained melamine fiber have higher breaking tenacity.
(5) add modified silicon oil in the present invention's reaction, except introducing soft segment, increase outside final fiber snappiness, resin system surface tension can be reduced, be conducive to the microbubble in deresinate.
(6) add softening agent in the present invention, decapacitation increases final fiber snappiness, can also improve the intermolecular reactive force of terpolycyantoamino-formaldehyde resin, be conducive to the stability of spinning process.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.
Embodiment 1:
Solid content is the synthesis of the modified melamine-formaldehyde formaldehyde resin of 80%
1. proportioning raw materials
2. synthesis technique
(1) successively raw material de-salted water good for said ratio, trimeric cyanamide, paraformaldehyde, benzoguanamine, Macrogol 200, sodium hydroxide are dropped into reactor.
(2) being arranged on pH value is under the condition of 10-10.5, and question response device chuck leads to hot water heating to 50-52 DEG C, insulation reaction 40 minutes; Question response device chuck leads to steam heating to 93-95 DEG C, and after material clear, add hydroxy silicon oil, sodium stearate, mixing speed is down to 40 revs/min, continues reaction 5.5 hours.
(3) in 1 hour, fast cooling is to 35-40 DEG C, and stopped reaction obtains modified melamine-formaldehyde resin.
(4) by the resin that obtains in step (3) after filtration, bubble removal step, remove impurity and microbubble in resin.
(5) spinning process is delivered to.
Embodiment 2:
Solid content is the synthesis of the modified melamine-formaldehyde formaldehyde resin of 75%
1. proportioning raw materials
2. synthesis technique
The step of preparation method is identical with embodiment 1, and after clear, add polyether modified silicon oil, stearic acid, mixing speed is down to 40 revs/min, continues reaction 5.0 hours.
Embodiment 3:
Solid content is the synthesis of the modified melamine-formaldehyde formaldehyde resin of 80%
1. proportioning raw materials
2. synthesis technique
Step is identical with embodiment 1, temperature of reaction 91-93 DEG C, and after clear, add hydroxy silicon oil, Zinic stearas, mixing speed is down to 40 revs/min, continues reaction 6.0 hours.
Embodiment 4
1. proportioning raw materials
The synthesis of 76% solid content modified melamine-formaldehyde formaldehyde resin
2. synthesis technique
Step is identical with embodiment 1, temperature of reaction 91-93 DEG C, and after clear, add methyl-silicone oil, tributyl phosphate, mixing speed is down to 40 revs/min, continues reaction 6.5 hours.
Embodiment 5:
Except not adding except Macrogol 200 in proportioning raw materials, other proportioning raw materials and synthesis technique are with embodiment 1.
Embodiment 6:
In proportioning raw materials except not adding first substituted melamine, other proportioning raw materials and synthesis technique are with embodiment 2.
Embodiment 7:
Except not adding except hydroxy silicon oil in proportioning raw materials, other proportioning raw materials and synthesis technique are with embodiment 3.
Final obtained resin after filtration, after bubble removal step, after testing, still have a large amount of microbubble in resin, can not spinning.
Embodiment 8
In proportioning raw materials except sodium hydroxide be 0.35kg, pH value is except 8.5-9, other proportioning raw materials and synthesis technique are with embodiment 3.
After reaction clear, add hydroxy silicon oil, Zinic stearas, mixing speed is down to 40 revs/min, and continue reaction 3.5 hours, resin viscosity rises rapidly, and become semi-cured state, resin is scrapped.
Embodiment 9
According to document " study on the modification of melamino-formaldehyde solvent impregnated resin ", whether can spinning by this resin of verification experimental verification.
1. proportioning raw materials
The synthesis of 60% solid content melamino-formaldehyde formaldehyde resin
2. synthesis technique
(1) successively de-salted water, trimeric cyanamide, liquid formaldehyde, glycol ether, hexanolactam, hexamethylenetetramine are dropped into reactor.
(2) reactor jacket leads to steam heating to 93-95 DEG C, and after material clear, insulation continues reaction 3.0 hours, and material is muddy.
(3) after fast cooling, material bleaches, and loses flowability.
Resin in this embodiment is widely used in wood-based plate surface impregnation paper, but because its degree of crosslinking degree is high, after molecular weight is increased to certain value, water-soluble variation, separates out from water, shows as resin and bleaches, therefore can not make melamine fiber by dry-spinning.
Embodiment gained melamine fiber salient features
From above experimental data: 1, common terpolycyantoamino-formaldehyde resin can not meet spinning requirement, as embodiment 9; 2, the reaction process impact of the pH value in reaction conditions on high solids content modified melamine-formaldehyde resin is large, such as embodiment 8, and when its pH value is lower, in reaction process, resin viscosity change is fast; Also spinning is unfavorable for; 3. modified silicon oil decapacitation is introduced outside soft segment, can reduce high solids content modified melamine-formaldehyde resin diagram of system surface tension, be conducive to the microbubble in deresinate, as embodiment 7 can not microbubble in deresinate; 4. properties-correcting agent is large on fibre property impact, as embodiment 5, embodiment 6 gained fiber can not meet post-treatment requirement.
Claims (9)
1. the preparation method for dry-spinning high solids content modified melamine-formaldehyde resin, it is characterized in that this modified melamine-formaldehyde resin comprises the raw material of following weight part: 10-100 parts of trimeric cyanamides, 15-600 part formaldehyde, 1-30 parts of properties-correcting agent, 1-30 parts of polymeric alcohols, 50-150 parts of de-salted waters, 0.1-5 parts of pH adjusting agents, 0.1-10 parts of modified silicon oils, 0.1-10 parts of softening agent; Specifically comprise the following steps:
The first step: raw material trimeric cyanamide, formaldehyde, properties-correcting agent, polymeric alcohol, de-salted water, pH adjusting agent, modified silicon oil and softening agent are carried out accurate measurement, then adds efficient strong-mixing reactor;
Second step, in efficient strong-mixing reactor, under higher pH condition, reacts: 30-60 DEG C of pre-reactions 20 minutes-1 hour at twice; React 3-7 hours under 80-95 DEG C of conditions;
3rd step, fast cooling cools, and stopped reaction obtains modified melamine-formaldehyde resin;
4th step, by the resin that obtains in the 3rd step after filtration, bubble removal step, remove impurity and microbubble in resin;
5th step, resin transfer is to spinning process.
2. the preparation method for dry-spinning high solids content modified melamine-formaldehyde resin according to claim 1, is characterized in that: the solid content of this modified melamine-formaldehyde resin is 60%-85%.
3. the preparation method for dry-spinning high solids content modified melamine-formaldehyde resin according to claim 1, is characterized in that: described formaldehyde is formaldehyde solution or paraformaldehyde; Described polymeric alcohol be in glycol ether, polyoxyethylene glycol, polypropylene glycol, polyvinyl alcohol, PTMG any one or multiple.
4. the preparation method for dry-spinning high solids content modified melamine-formaldehyde resin according to claim 1, is characterized in that: described properties-correcting agent is containing any one or a few the mixture in the pyrrolotriazine derivatives of alkyl, aralkyl, terminal hydroxy group.
5. the preparation method for dry-spinning high solids content modified melamine-formaldehyde resin according to claim 1, is characterized in that: described pH adjusting agent is any one or a few the mixture in inorganic alkaline thing or organic amine.
6. the preparation method for dry-spinning high solids content modified melamine-formaldehyde resin according to claim 1, is characterized in that: described modified silicon oil is any one or a few the mixture in methyl-silicone oil, hydroxy silicon oil or polyether modified silicon oil.
7. the preparation method for dry-spinning high solids content modified melamine-formaldehyde resin according to claim 1, is characterized in that: described softening agent is any one or a few the mixture in phosphoric acid ester, soap or fatty acid ester.
8. the preparation method for dry-spinning high solids content modified melamine-formaldehyde resin according to claim 1, is characterized in that: described efficient strong-mixing reactor is multiaxis planet stirring reactor or screw reactor.
9. the preparation method for dry-spinning high solids content modified melamine-formaldehyde resin according to claim 1, is characterized in that: the pH value of described higher pH condition is 8.5-12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410351095.1A CN104140511B (en) | 2014-07-23 | 2014-07-23 | For dry-spinning high solids content modified melamine-formaldehyde resin and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410351095.1A CN104140511B (en) | 2014-07-23 | 2014-07-23 | For dry-spinning high solids content modified melamine-formaldehyde resin and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104140511A CN104140511A (en) | 2014-11-12 |
| CN104140511B true CN104140511B (en) | 2015-11-18 |
Family
ID=51849860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410351095.1A Active CN104140511B (en) | 2014-07-23 | 2014-07-23 | For dry-spinning high solids content modified melamine-formaldehyde resin and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104140511B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356594B (en) * | 2014-11-27 | 2016-05-25 | 长春工业大学 | A kind of preparation method of organosilicon melamine resin compound particle |
| CN104831373B (en) * | 2015-06-04 | 2017-01-18 | 四川金象赛瑞化工股份有限公司 | Melamine fiber dry spinning method |
| CN105002593A (en) * | 2015-07-10 | 2015-10-28 | 东华大学 | Nano-material-modified melamine fiber preparation method |
| CN106192156A (en) * | 2016-08-26 | 2016-12-07 | 明光市瑞洁日用品有限公司 | A kind of fungi-proofing fiber cloth |
| CN106167925A (en) * | 2016-09-14 | 2016-11-30 | 郑州峰泰纳米材料有限公司 | High intensity melamino-formaldehyde resin fibre and preparation method thereof |
| CN106167924A (en) * | 2016-09-14 | 2016-11-30 | 郑州峰泰纳米材料有限公司 | Flame retardant type melamino-formaldehyde resin fibre and preparation method thereof |
| CN106319682A (en) * | 2016-09-14 | 2017-01-11 | 郑州峰泰纳米材料有限公司 | Melamino-formaldehyde resin fiber and preparation method thereof |
| CN106245152A (en) * | 2016-09-14 | 2016-12-21 | 郑州峰泰纳米材料有限公司 | Uvioresistant melamino-formaldehyde resin fibre and preparation method thereof |
| CN106381572A (en) * | 2016-09-14 | 2017-02-08 | 郑州峰泰纳米材料有限公司 | High-dielectric-constant melamine resin fiber and preparation method thereof |
| CN107475857A (en) * | 2017-09-14 | 2017-12-15 | 储旭 | A kind of antibiotic facing material and preparation method thereof |
| CN109457314A (en) * | 2018-10-31 | 2019-03-12 | 谢国宝 | A kind of spinning solution and preparation method thereof for producing viscose rayon |
| CN109881293B (en) * | 2019-03-28 | 2020-06-23 | 四川大学 | Melamine composite fiber and manufacturing method thereof |
| CN114622298B (en) * | 2020-12-10 | 2023-08-25 | 中原工学院 | Method for preparing thermosetting melamine fiber through dry spinning |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1344821A (en) * | 2001-06-26 | 2002-04-17 | 天津工业大学 | Fire-retardant fiber and its making process |
| CN101016658A (en) * | 2007-01-15 | 2007-08-15 | 四川大学 | Method of preparing melamine formaldehyde resin/polyvinyl alcohol flame-proof fiber |
-
2014
- 2014-07-23 CN CN201410351095.1A patent/CN104140511B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1344821A (en) * | 2001-06-26 | 2002-04-17 | 天津工业大学 | Fire-retardant fiber and its making process |
| CN101016658A (en) * | 2007-01-15 | 2007-08-15 | 四川大学 | Method of preparing melamine formaldehyde resin/polyvinyl alcohol flame-proof fiber |
Non-Patent Citations (1)
| Title |
|---|
| 三聚氰胺纤维改性及工艺研究;毕慧平;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》;20041215(第04期);B016-220 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104140511A (en) | 2014-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104140511B (en) | For dry-spinning high solids content modified melamine-formaldehyde resin and preparation method | |
| CN101250374B (en) | Nano hollow silica dioxide micro-sphere/polyurethane composite aqueous paint and preparation method thereof | |
| CN103382253B (en) | A kind of high-performance water-based polyurethane dispersoid and preparation method thereof | |
| CN105925168A (en) | Microencapsulated water-based fire retardant coating and preparation method thereof | |
| CN108003332B (en) | Easily hydrolyzed polyester and synthesis method thereof | |
| CN1995130A (en) | Halogen-free environment-friendly flame-proof polyoxymethylene resin and its preparation method | |
| CN100412068C (en) | 2-amino ethyl sulfonic acid modified water epoxy resin and its preparation method and water epoxy emulsion prepared from said water epoxy resin | |
| CN109112666A (en) | A method of phenolic fibre is prepared by wet spinning | |
| CN105482052A (en) | Thermosetting resin and preparation method | |
| CN105693984A (en) | Method for preparing waterborne polyurethane containing imide ring | |
| CN107602809B (en) | High-solid-content aqueous polyurethane dispersion liquid based on aminocarboxylate and sulfamate simultaneously | |
| CN103408717A (en) | Preparation method of terminated water-based polyamine resin | |
| CN113968978A (en) | Novel nano lignin and preparation method thereof | |
| CN111662530A (en) | Halogen-free flame-retardant epoxy resin system for prepreg and preparation method thereof | |
| CN110627979A (en) | Hydroxymethylated melamine formaldehyde resin and preparation method and application thereof | |
| CN103772640A (en) | Flame-retardant wood adhesive as well as preparation method and application thereof | |
| Cheng et al. | Synthesis of a novel boron‐containing hyperbranched benzoxazine and its flame‐retardant properties in copolymer with epoxy resin | |
| CN107163076B (en) | Phosphorus-Containing Triazine salt compound and its preparation method and application | |
| CN105085887B (en) | Anti-ultraviolet polyester film | |
| CN105732971B (en) | A kind of halogen-free environmental carbon forming agent preparation method and application | |
| CN109776861B (en) | Intumescent flame retardant taking ethylene glycol modified melamine formaldehyde resin as char forming agent | |
| CN114426678B (en) | Lignin-based flame-retardant charring agent and synthetic method and application thereof | |
| CN110105626B (en) | Supermolecular assembly modified ammonium polyphosphate and preparation method thereof | |
| CN103319671A (en) | Preparation method of phenolic resin for refractory material | |
| CN113755083A (en) | Preparation method of solvent-free polyurea coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |