CN103554399B - Phosphorus-containing binding resin and synthetic method thereof - Google Patents
Phosphorus-containing binding resin and synthetic method thereof Download PDFInfo
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- CN103554399B CN103554399B CN201310476147.3A CN201310476147A CN103554399B CN 103554399 B CN103554399 B CN 103554399B CN 201310476147 A CN201310476147 A CN 201310476147A CN 103554399 B CN103554399 B CN 103554399B
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- resorcinol
- phenol
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- binder resin
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Abstract
The invention provides a phosphorus-containing binding resin having a structural formula shown in the description.
Description
Technical field
The present invention relates to rubber industry resin art, relate to a kind of binder resin and synthetic method thereof specifically.
Background technology
Resorcinol-formaldehyde resin is the conventional steel wire cord of rubber tyre industry and the tackiness agent between polyester cord and rubber, and it produces adhesive effect by reacting with methylene radical donor, for the bonding of rubber and framework material.It containing free formaldehyde, does not have very low vapour pressure, greatly reduces the problem using Resorcinol monomer to reduce higher than the cigarette occurred when 150 DEG C and weight in processing temperature.
The price of Resorcinol remains high always, and by several major company, particularly several corporation with foreign capital monopolized, and raw material sources are limited, substantially increases production cost.And the free Resorcinol content of resorcinol-formaldehyde resin remnants is still very high, general all about 10%, therefore resorcinol-formaldehyde resin in use (general more than 150 DEG C) also have free Resorcinol and evaporate, bring harm to environment and human body.
The synthesis technique of P-F binder resin is simple, and raw material is easy to get, and the cost ratio Resorcinol of phenol is much lower.But its bond properties is lower than Resorcinol, and ageing-resistant performance is bad, reason is that its activity is lower, the solid netted crosslinking structure of more difficult formation.
Summary of the invention
The object of the present invention is to provide a kind of phosphorous binder resin, the structural formula of this binder resin is:
Wherein n is more than or equal to 1,
R is methyl, ethyl, propyl group and amino.
Present invention also offers a kind of phosphorous binder resin, it prepares by the following method:
(1) by phenol, Resorcinol, formaldehyde, sodium hydroxide according to mol ratio 1:(0-2): (1-3): (0.01-0.1) is placed in reactor, 80-90 DEG C reaction 1-3 hour;
(2) in above-mentioned mixed solution, add organic phospho acid, the mol ratio of phenol and Resorcinol sum and organic phospho acid is 1:(0.05-0.2), be warmed up to 110-180 DEG C, continue reaction 1-20 hour;
(3) reaction kettle for vacuumizing, removes water and low molecular compound, namely obtains phosphorous binder resin.
Organic phospho acid wherein used is properties-correcting agent, includes but not limited to hydroxy ethylene diphosphonic acid, hydroxymethyl phosphonic acid, ethylenediamine tetramethylene phosphonic acid, Amino Trimethylene Phosphonic Acid, diethylene triamine pentamethylene phosphonic or hexapotassium.
Present invention also offers the method preparing aforementioned phosphorous binder resin, the method comprises the steps:
(1) by phenol, Resorcinol, formaldehyde, sodium hydroxide according to mol ratio 1:(0-2): (1-3): (0.01-0.1) is placed in reactor, 80-90 DEG C reaction 1-3 hour;
(2) in above-mentioned mixed solution, add organic phospho acid, the mol ratio of phenol and Resorcinol sum and organic phospho acid is 1:(0.05-0.2), be warmed up to 110-180 DEG C, continue reaction 1-20 hour;
(3) reaction kettle for vacuumizing, removes water and low molecular compound, namely obtains phosphorous binder resin.
Concrete reaction process is as follows:
Principle of the present invention is with phenol moieties or replaces Resorcinol synthetic resin adhesive completely, significantly reduces cost on the one hand, and on the other hand because Resorcinol consumption reduces and process improving, product residue Resorcinol content also significantly reduces, and flue gas reduces.
The present invention the most important thing is the modification by a special organic phospho acid, improve the activity of resol, by multiple functional groups of organic phospho acid, enhance stereo crosslinked network structure, thus substantially increase bond properties and the ageing-resistant performance of resin, reach the performance more excellent than resorcinol-formaldehyde resin.
This rosin products has following advantage:
(1) this product can replace the bonding of resorcinol-formaldehyde resin for rubber and framework material;
(2) this product cost is more much lower than resorcinol-formaldehyde resin;
(3) this product Resorcinol content that dissociates is few, environmental protection more;
Embodiment
Embodiment below in conjunction with embodiment is described in further detail foregoing of the present invention again, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following example.
Embodiment 1
(1) take starting material according to phenol 1 mole, Resorcinol 1.5 moles, 2.5 moles, formaldehyde, 0.05 mole, sodium hydroxide, above-mentioned starting material are joined in reactor, is heated to 80 DEG C, stirs with agitator, react 3 hours at 80 DEG C;
(2) temperature of reaction kettle is elevated to 130 DEG C, and adds hydroxy ethylene diphosphonic acid 0.25 mole, continue reaction 10 hours in reactor, and constantly stir;
(3) vacuumize dehydration, then the thick liquid in reactor is poured out, be the binder resin of organic phospho acid modification.
Embodiment 2
(1) take starting material according to phenol 2 moles, Resorcinol 2 moles, 4 moles, formaldehyde, 0.1 mole, sodium hydroxide, above-mentioned starting material are joined in reactor, is heated to 85 DEG C, stirs with agitator, react 2 hours at 85 DEG C;
(2) temperature of reaction kettle is elevated to 150 DEG C, and adds Amino Trimethylene Phosphonic Acid 0.4 mole, continue reaction 6 hours in reactor, and constantly stir;
(3) vacuumize dehydration, then the thick liquid in reactor is poured out, be the binder resin of organic phospho acid modification.
Embodiment 3
(1) take starting material according to phenol 4 moles, 4 moles, formaldehyde, 0.05 mole, sodium hydroxide, starting material are joined in reactor, be heated to 90 DEG C, stir with agitator, react 1 hour at 90 DEG C;
(2) temperature of reaction kettle is elevated to 140 DEG C, and adds diethylene triamine pentamethylene phosphonic 0.5 mole, continue reaction 8 hours in reactor, and constantly stir;
(3) vacuumize dehydration, then the thick liquid in reactor is poured out, be the binder resin of organic phospho acid modification.
Embodiment 4 bond properties is tested
According to standard GB/T 3513-2001, carry out bond properties experiment.Formula with reference to lower list 1 carries out bond properties experiment, in order to check the bond properties of binder resin.Following formula is conventional all-steel radial tire steel wire adhesive formula, for the wirecord fabric of all-steel radial tire.
Table 1 bond properties experimental formula
| Starting material | Formula 1# | Formula 2# | Formula 3# |
| Natural rubber | 100.00 | 100.00 | 100.00 |
| Carbon black N326 | 50.00 | 50.00 | 50.00 |
| White carbon black | 10.00 | 10.00 | 10.00 |
| Stearic acid | 1.00 | 1.00 | 1.00 |
| Zinc oxide | 8.00 | 8.00 | 8.00 |
| 6PPD | 1.50 | 1.50 | 1.50 |
| RD | 1.00 | 1.00 | 1.00 |
| Cobalt boracylate | 0.50 | 0.50 | 0.50 |
| HMM-65 | 5.00 | 5.00 | 5.00 |
| ISOT20 | 5.00 | 5.00 | 5.00 |
| NS | 1.00 | 1.00 | 1.00 |
| A | 2.5 | ||
| B | 2.5 | ||
| C | 2.5 |
Note: A is unmodified phenol-formaldehyde resin (205 resins, Taiyuan Yuan Tai biochemical industry company limited product)
B is resorcinol-formaldehyde resin (RF-90, Changzhou Chang Jing Chemical Co., Ltd. product)
C is the phenol-formaldehyde resin (embodiment 3 product) of organic phospho acid modification
Experimental result is in table 2.
Table 2 bond properties experimental result
| Performance index | Formula 1# | Formula 2# | Formula 3# |
| Hardness/Shao Er A | 78 | 74 | 74 |
| 50% stretches/MPa surely | 2.66 | 2.85 | 2.76 |
| 100% stretches/MPa surely | 3.62 | 4.25 | 4.15 |
| 300% stretches/MPa surely | 13.5 | 15.8 | 15.1 |
| Tsb/MPa | 24.1 | 25.8 | 25.1 |
| Eb/％ | 488 | 431 | 436 |
| Aging front steel wire extraction/N | 784 | 938 | 945 |
| Aging front rubber coating rate/% | 80 | 90 | 90 |
| Aging rear steel wire extraction/N | 585 | 846 | 856 |
| Aging rear rubber coating rate/% | 60 | 85 | 85 |
Note: aging condition: 100 DEG C of * 48h
The content of the free Resorcinol in the RF-90 resin recorded by high performance liquid chromatography (HPLC) is 8%, and modification and unmodified phenol-formaldehyde resin be not containing Resorcinol.
As can be seen from above data, the bounding force of unmodified phenol-formaldehyde resin is significantly less than resorcinol-formaldehyde resin, and aging after bounding force reduce obviously; And the modified resin of organic phospho acid has the bond properties suitable with resorcinol-formaldehyde resin, and its free Resorcinol content is lower, more environmental protection.
Claims (1)
1. prepare a method for phosphorous binder resin, it is characterized in that the method comprises the steps:
(1) by phenol, Resorcinol, formaldehyde, sodium hydroxide according to mol ratio 1:(0-2): (1-3): (0.01-0.1) is placed in reactor, 80-90 DEG C reaction 1-3 hour;
(2) in above-mentioned mixed solution, add organic phospho acid, the mol ratio of phenol and Resorcinol sum and organic phospho acid is 1:(0.05-0.2), be warmed up to 110-180 DEG C, continue reaction 1-20 hour;
(3) reaction kettle for vacuumizing, removes water and low molecular compound, namely obtains phosphorous binder resin;
Wherein said organic phospho acid is hydroxy ethylene diphosphonic acid, Amino Trimethylene Phosphonic Acid.
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| CN107459614B (en) * | 2017-08-28 | 2019-07-26 | 上海超程化工科技有限公司 | A kind of environment-friendly type adhesion promotor and preparation method thereof, application |
| CN111730697B (en) * | 2020-07-08 | 2022-04-19 | 百草边大生物科技(青岛)有限公司 | Wormwood modified veneer and preparation method thereof |
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| CN101565490A (en) * | 2009-04-29 | 2009-10-28 | 山东莱芜润达化工有限公司 | Method for producing environment-friendly high-performance novolac resin |
| CN102066445A (en) * | 2008-06-12 | 2011-05-18 | 日立化成工业株式会社 | Manufacturing method for phenolic novolac resin and resin-coated sand |
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| JP2011122009A (en) * | 2009-12-08 | 2011-06-23 | Sumitomo Bakelite Co Ltd | Drying oil-modified resol type phenolic resin, phenolic resin composition, prepreg, and laminated board |
| JP5426436B2 (en) * | 2010-03-11 | 2014-02-26 | 関西ペイント株式会社 | Modified phenolic resin and aqueous coating composition containing the same |
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| CN102066445A (en) * | 2008-06-12 | 2011-05-18 | 日立化成工业株式会社 | Manufacturing method for phenolic novolac resin and resin-coated sand |
| CN101565490A (en) * | 2009-04-29 | 2009-10-28 | 山东莱芜润达化工有限公司 | Method for producing environment-friendly high-performance novolac resin |
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Effective date of registration: 20171027 Address after: 223005 Huaian city of Jiangsu province Huaian salinization New Material Industrial Park No. 19 Wan Li Patentee after: Jiangsu Qixiang New Material Co., Ltd. Address before: 201802 Shanghai Jiading District Nanxiang really Road South Town No. 4929 room 617 Patentee before: SHANGHAI CHEESHINE CHEMICALS CO., LTD. |