CN101230121A - Preparation method of tall oil modified alkyd resin - Google Patents
Preparation method of tall oil modified alkyd resin Download PDFInfo
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- CN101230121A CN101230121A CNA2007101689651A CN200710168965A CN101230121A CN 101230121 A CN101230121 A CN 101230121A CN A2007101689651 A CNA2007101689651 A CN A2007101689651A CN 200710168965 A CN200710168965 A CN 200710168965A CN 101230121 A CN101230121 A CN 101230121A
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Abstract
The invention relates to a preparation method for tall oil-modified phenolic resin. The resin comprises the following components according to parts by weight: 90 to 100 shares of phenol, 6 to 9 shares of tert butylphenol, 55 to 65 shares of formaldehyde with 37 percent content, 0.4 to 0.5 shares of oxalic acid, 30 to 40 shares of tall oil, 8 to 10 shares of colophony, and 0.1 to 0.2 shares of hexa (4-aldehyde phenoxy) cyclic triphosphonitrile The invention adopts the brand-new production method of the technology of tall oil-modified phenolic resin, with simple process. The production cost is not increased, compared with the prior product, the product performance is greatly improved (reaching about 20 percent), and the product performance achieves or exceeds the performance of similar foreign products.
Description
Technical field
The present invention relates to a kind of preparation method of tall oil modified alkyd resin.
Technical background
Strengthening agent is meant the auxiliary agent that can improve sizing material hardness, dynamic modulus, improving sizing material hardness traditionally is with the ratio that strengthens reinforced filling (as carbon black), but this method can be brought the series of process problem, and can damage other performance, can avoid these problems and use reinforced resin to improve hardness.Strengthening agent comprises kinds such as high styrene resin, resol, tall oil modified resin, cashew nut oil modified resin.High styrene resin can with rubber generation covulcanization, but price is higher, and thermotolerance is relatively poor, is mainly used at present in the non-staining sundry goods.The industry of tire industry, rubber roll is main uses the reinforcement of phenolic reinforced resin, and such strengthening agent forms inierpeneirating network structure (IPN) with the rubber cross network when sulfuration, utilizes the rigidity of phenolic aldehyde network and two network interpenetratings to superpose and reaches the purpose of reinforcement.But resol fragility is big, water-intake rate is high, oil soluble is poor, and poor with the compatibility of polymkeric substance and solvent.Oil-modified resin has reduced the polarity of resol, has strengthened interpenetrating(polymer)networks density, the easier rubber that is scattered in, and reinforcing effect is better.
Tall oil modified alkyd resin is a kind of thermoplastic elastomer reinforced resin, compare with common non-modified resin, good plasticity is arranged in the course of processing, good with rubber compatibility, reinforcement hardness improves 5～10%, can improve the tearing of sizing material, wear resistance, powerful with stretch performance surely, prolong time of scorch, reduction sizing material mooney viscosity.Can be used for tire bead position, tyre surface, also can be used for products such as vehicle window sealed strip, conveying belt, wire belt, especially application is wider in radial triangle glue, makes the endurance quality of finished tire surpass national standard-required.
Yet the product of domestic production is compared with imported product, and time of scorch is obviously short partially, sizing material is vulcanized in advance, can not well satisfy rubber processing, can only be applied in the low side rubber products such as walkie fork lift truck, and high-end doughnut manufacturing enterprise mainly uses imported product.So, improve the production technique that has tall oil modified alkyd resin now, enhance product performance, it is reached even be better than the performance of external product, improve the competitive power of domestic relevant enterprise, very necessary, also help promoting the development of China's functional rubber auxiliary agent industry.
Summary of the invention
In order to overcome the low deficiency that waits of currently available products coke burning performance, the invention provides a kind of preparation method of tall oil modified alkyd resin.It to enhance product performance, makes its coke burning performance satisfy the doughnut rubber processing by improving the production technique of existing tall oil modified alkyd resin, reaches the imported product peer-level.
A kind of preparation method of tall oil modified alkyd resin is characterized in that it comprises following component, and consumption is a weight part,
Phenol: 90～100 parts, tertiary butyl phenol: 6～9 parts, the formaldehyde of content 37%: 55～65 parts, oxalic acid: 0.4～0.5 part, Yatall MA: 30～40 parts, rosin: 8～10 parts, six (4-aldehyde radical phenoxy group) ring, three phosphonitriles: 0.1～0.2,
Its preparation method is as follows:
(1), to phenol, tertiary butyl phenol, the catalyzer of reactor input metering, slowly be warming up to 45～55 ℃, stop to heat up;
(2), stirred 10～20 minutes, under reflux state, begin to drip formaldehyde, added in 1～1.5 hour, added the back back flow reaction 3 hours, keep 95～102 ℃ of temperature;
(3), reflux state is adjusted to dewatering state, the dehydration that heats up is warming up to 120～130 ℃ and stops to heat up, and stirs 15～30 minutes;
(4), heat up, keep dewatering state, begin to drip rosinol in 155～160 ℃, added in 20～30 minutes;
(5), continue reaction 1 hour, adding six (4-aldehyde radical phenoxy groups) ring three phosphonitriles, vacuum hydro-extraction 10～30 minutes, vacuum tightness＞0.085MPa in 170～180 ℃; Discharging.
The preparation method of described rosinol is: the Yatall MA, rosin that drop into metering successively in dripping still, be warming up to 130～150 ℃ standby.
The preparation method of a kind of tall oil modified alkyd resin of the present invention has following advantage: 1, and synthesis technique adopts brand-new tall oil modified alkyd resin explained hereafter method, and technology is simple.2, do not increase production cost, product performance are compared improve a lot (reaching about 20%) with currently available products, meet or exceed the performance of external like products.
Embodiment
Describe performance of the present invention in detail below by embodiment, but they do not constitute limitation of the invention, simultaneously by illustrating that advantage of the present invention will become clear more and understanding easily.
Embodiment 1
Add 90g phenol, 6g tertiary butyl phenol, catalyzer (oxalic acid) 0.4g in the there-necked flask of 500mL, be warmed up to 50 ℃, after stirring, drip 37% formaldehyde 55g under reflux state, add about 1 hour, 102 ℃ were refluxed 3 hours.When the dehydration that heats up, 110 ℃ of systems, bleach continues to be warming up to 130 ℃, stops to heat up, and stirs 15 minutes, and the maintenance dewatering state that heats up begins to drip rosinol 38g (30g Yatall MA and 8g rosin shift to an earlier date heat fused) in 160 ℃, adds in 30 minutes.180 ℃ are continued reaction 1 hour, add N
3P
3(OC
6H
4CHO)
60.1g, vacuum hydro-extraction 30 minutes (vacuum tightness＞0.085MPa), stopped reaction is poured out material, after cold reddish-brown transparent sheet-like solid.
Embodiment 2
Add 100g phenol, 9g tertiary butyl phenol, catalyzer (oxalic acid) 0.5g in the there-necked flask of 1L, be warmed up to 50 ℃, after stirring, drip 37% formaldehyde 65g under reflux state, added in 1 hour 10 minutes, 102 ℃ were refluxed 3 hours.When the dehydration that heats up, 110 ℃ of systems, bleach continues to be warming up to 130 ℃, stops to heat up, and stirs 15 minutes, and the maintenance dewatering state that heats up begins to drip rosinol 50g (40g Yatall MA and 10g rosin shift to an earlier date heat fused) in 160 ℃, adds in 30 minutes.180 ℃ are continued reaction 1 hour, add N
3P
3(OC
6H
4CHO)
60.2g, vacuum hydro-extraction 30 minutes (vacuum tightness＞0.085MPa), stopped reaction is poured out material, after cold reddish-brown transparent sheet-like solid.
Embodiment 3
Add 95kg phenol, 7.5kg tertiary butyl phenol, catalyzer (oxalic acid) 0.45g in the reactor of 200L, be warmed up to 50 ℃, open and stir, drip 37% formaldehyde 60kg under reflux state, added in 1 hour 30 minutes, 102 ℃ were refluxed 3 hours.After reaction finishes, reflux state is adjusted to dewatering state, be warming up to 130 ℃, stop to heat up, stirred 15 minutes, continuing to heat up keeps dewatering state, and (35kg Yatall MA and 9kg rosin add in the dropping still in advance to begin to drip rosinol 44kg in 160 ℃, be warming up to 130～150 ℃), added in 30 minutes.Be warmed up to 180 ℃ and continue reaction 1 hour, add N
3P
3(OC6H4CHO)
60.15g (vacuum tightness＞0.085MPa), discharging got reddish-brown transparent sheet-like solid in 30 minutes in vacuum hydro-extraction.
Embodiment 4
In the 1000L reactor, add 90kg phenol, 8kg tertiary butyl phenol, catalyzer (oxalic acid) 0.4kg, be warmed up to 50 ℃, open and stir, under reflux state, drip 37% formaldehyde 60kg, added in 1 hour 30 minutes, 102 ℃ of back flow reaction 3 hours.After reaction finishes, reflux state is adjusted to dewatering state, be warming up to 130 ℃, stop to heat up, stirred 15 minutes, continuing to heat up keeps dewatering state, and (40kg Yatall MA and 9kg rosin add in the dropping still in advance to begin to drip rosinol 49kg in 160 ℃, be warming up to 130～150 ℃), added in 30 minutes.Be warmed up to 180 ℃ and continue reaction 1 hour, add N
3P
3(OC
6H
4CHO)
60.2g (vacuum tightness＞0.085MPa), discharging got reddish-brown transparent sheet-like solid in 30 minutes in vacuum hydro-extraction.
Product quality indicator test of the present invention is as follows:
1. the test of free phenol is tested with bromination method: the test free phenol is 0.05～0.5%.
2. the physico-chemical analysis result of resin
| Test item | |
| Outward appearance weight loss on heating (65 ℃ of * 2h)/% ash content massfraction softening temperature (ring and ball method)/℃ | Reddish-brown sheet 0.07 0.09 97.5 |
3. big cooperation properties of rubber (with domestic currently available products contrast)
| Test item | Domestic currently available products | Embodiment 2 products | Embodiment 3 products | Embodiment 4 products |
| Tensile strength Mpa tensile yield % 100% stretches Mpa 300 surely and stretches Mpa tear strength N/mm hardness Shao Er A IRHD proportion cm surely 3/ g resilience % carbon black dispension degree Mooney ML (127 ℃ of @100 ℃ of incipient scorch of 1+4) | 15.9 256 7.4 - 59.1 89 100 1.159 21 5.3 56.2 20∶13 | 15.8 252 7.5 - 58.2 91 100 1.157 24 5.7 60.6 24∶09 | 15.9 249 7.5 - 57.8 92 100 1.158 24 5.6 59.8 23∶58 | 15.8 251 7.4 - 58.3 91 100 1.158 24 5.7 60.1 24∶17 |
Claims (1)
1. the preparation method of a tall oil modified alkyd resin is characterized in that it comprises following component, and consumption is a weight part,
Phenol: 90～100 parts, tertiary butyl phenol: 6～9 parts, the formaldehyde of content 37%: 55～65 parts, oxalic acid: 0.4～0.5 part, Yatall MA: 30～40 parts, rosin: 8～10 parts, six (4-aldehyde radical phenoxy group) ring, three phosphonitriles: 0.1～0.2,
Its preparation method is as follows:
(1), to phenol, tertiary butyl phenol, the catalyzer of reactor input metering, slowly be warming up to 45～55 ℃, stop to heat up;
(2), stirred 10～20 minutes, under reflux state, begin to drip formaldehyde, added in 1～1.5 hour, added the back back flow reaction 3 hours, keep 95～102 ℃ of temperature;
(3), reflux state is adjusted to dewatering state, the dehydration that heats up is warming up to 120～130 ℃ and stops to heat up, and stirs 15～30 minutes;
(4), heat up, keep dewatering state, begin to drip rosinol in 155～160 ℃, added in 20～30 minutes;
(5), continue reaction 1 hour, adding six (4-aldehyde radical phenoxy groups) ring three phosphonitriles, vacuum hydro-extraction 10～30 minutes, vacuum tightness＞0.085MPa in 170～180 ℃; Stopped reaction is poured out material, gets reddish-brown transparent sheet-like solid after the cooling, is tall oil modified alkyd resin of the present invention
The preparation method of described rosinol is: the Yatall MA, rosin that drop into metering successively in dripping still, be warming up to 130～150 ℃ standby.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101689651A CN101230121B (en) | 2007-12-20 | 2007-12-20 | Preparation method of tall oil modified alkyd resin |
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| CN2007101689651A CN101230121B (en) | 2007-12-20 | 2007-12-20 | Preparation method of tall oil modified alkyd resin |
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| CN101230121A true CN101230121A (en) | 2008-07-30 |
| CN101230121B CN101230121B (en) | 2010-06-02 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798374B (en) * | 2010-01-18 | 2012-05-02 | 太原化学工业集团技术中心 | Modified phenolic resin and manufacture method thereof |
| CN102634081A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Anti-aging lower bead filler rubber composition for all steel radial tire |
| CN103910841A (en) * | 2013-01-09 | 2014-07-09 | 华奇（张家港）化工有限公司 | Tall oil modified phenolic resin and preparation method thereof |
| CN103910842A (en) * | 2013-01-09 | 2014-07-09 | 华奇（张家港）化工有限公司 | Tall oil modified phenolic resin and preparation method and application thereof |
| CN105254854A (en) * | 2015-11-17 | 2016-01-20 | 北京彤程创展科技有限公司 | Resin for improving rubber tear resistance, preparation method and application of resin |
| CN105330907A (en) * | 2015-12-08 | 2016-02-17 | 北京彤程创展科技有限公司 | Rubber composition for improving tearing property of rubber and application |
| CN109608600A (en) * | 2018-12-04 | 2019-04-12 | 镇江利德尔复合材料有限公司 | A kind of heat-resisting material for power plant is resin dedicated and preparation method thereof |
| CN110527041A (en) * | 2019-10-12 | 2019-12-03 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of phenolic resin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035258C (en) * | 1991-11-05 | 1997-06-25 | 成都科技大学 | Preparation and application of tung oil modified linear phenol-aldehyde resin |
| CN1817929A (en) * | 2006-03-13 | 2006-08-16 | 覃强 | Process for producing phenolic resin by secondary throwing method |
-
2007
- 2007-12-20 CN CN2007101689651A patent/CN101230121B/en active Active
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798374B (en) * | 2010-01-18 | 2012-05-02 | 太原化学工业集团技术中心 | Modified phenolic resin and manufacture method thereof |
| CN102634081A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Anti-aging lower bead filler rubber composition for all steel radial tire |
| CN103910841A (en) * | 2013-01-09 | 2014-07-09 | 华奇（张家港）化工有限公司 | Tall oil modified phenolic resin and preparation method thereof |
| CN103910842A (en) * | 2013-01-09 | 2014-07-09 | 华奇（张家港）化工有限公司 | Tall oil modified phenolic resin and preparation method and application thereof |
| CN103910841B (en) * | 2013-01-09 | 2016-04-06 | 华奇（张家港）化工有限公司 | A kind of tall oil modified alkyd resin and preparation method thereof |
| CN103910842B (en) * | 2013-01-09 | 2016-08-03 | 华奇（中国）化工有限公司 | A kind of tall oil modified alkyd resin and its preparation method and application |
| CN105254854A (en) * | 2015-11-17 | 2016-01-20 | 北京彤程创展科技有限公司 | Resin for improving rubber tear resistance, preparation method and application of resin |
| CN105330907A (en) * | 2015-12-08 | 2016-02-17 | 北京彤程创展科技有限公司 | Rubber composition for improving tearing property of rubber and application |
| CN105330907B (en) * | 2015-12-08 | 2017-12-08 | 北京彤程创展科技有限公司 | Improve rubber composition and the application of rubber tear resistance |
| CN109608600A (en) * | 2018-12-04 | 2019-04-12 | 镇江利德尔复合材料有限公司 | A kind of heat-resisting material for power plant is resin dedicated and preparation method thereof |
| CN110527041A (en) * | 2019-10-12 | 2019-12-03 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of phenolic resin |
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|---|---|
| CN101230121B (en) | 2010-06-02 |
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