CN102199265B - Long carbon chain nylon modified phenolic resin and preparation method thereof - Google Patents
Long carbon chain nylon modified phenolic resin and preparation method thereof Download PDFInfo
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- CN102199265B CN102199265B CN201110075217A CN201110075217A CN102199265B CN 102199265 B CN102199265 B CN 102199265B CN 201110075217 A CN201110075217 A CN 201110075217A CN 201110075217 A CN201110075217 A CN 201110075217A CN 102199265 B CN102199265 B CN 102199265B
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Abstract
The invention discloses long carbon chain nylon modified phenolic resin and a preparation method thereof. The method comprises the following steps of: mixing long carbon chain nylon, phenol and an acid catalyst, heating to dissolve the long carbon chain nylon, dripping aqueous solution of formaldehyde with stirring, controlling the reaction temperature to be 94-102DEG C, reacting for 2 to 5 hours after the dripping is finished, purifying and drying, wherein the total number of carbon atoms in two carbon chains connected by an amido bond in the long carbon chain nylon is not less than 16. The method has the advantages of improving toughness of modified phenolic resin, reducing water absorbability of the modified phenolic resin, saving energy, reducing consumption, along with mild reaction conditions, narrow molecular weight distribution and moderate viscosity of the modified phenolic resin, no special requirement on production equipment and the like, and is suitable for industrial production.
Description
Technical field
The present invention relates to thermosetting resin and method of modifying thereof, be specifically related to a kind of long carbon chain nylon modified phenolic resins and preparation method thereof.
Background technology
Resol is first kind of synthetic polymer on the complete meaning; With its excellent thermotolerance, flame retardant resistance, mechanical strength; And have concurrently than lower production cost, be widely used in fields such as making matrix material, wood binder, coating, friction materials, cellular insulant and ablation friction materials.
Yet resol is after solidifying, because its degree of crosslinking is very high, the segmental rigidity is big, causes easy to crack, the poor toughness of goods after the moulding, has limited in some Application for Field.Therefore, the toughness that improves resol and matrix material thereof through appropriate means is a major issue that need solve in industry member and academia, and is simultaneously, also significant with the added value of its derived product of increase to the class that promotes phenolic resin composite.
At present, improve the main means of resol flexible and be: fill or blending and modifying with rubber, nano particle, layered silicate, thermoplastic resin, yet, also exist some problems.For example, the molecular weight of rubber is high, a little less than the polarity, cause the consistency between they and the resol poor, and its dispersion state in resol also is difficult to by control preferably.
Therefore, modified rubber is difficult to play the ideal toughening effect sometimes, also can cause problems such as modified phenolic resins viscosity height and thermotolerance reduction simultaneously; Nanometer inorganic filler is prone to reunite, be difficult to homodisperse in resol; Thermoplastic resin and resol blend energy consumption are higher, and consumption is big.Therefore, the key that addresses the above problem is to develop the method for more effective modified phenolic resins, should guarantee toughening effect like this, and easy realization of industrial is amplified again.
Have certain practical value with nylon modified phenolic resin, the toughness of nylon is better, and is better with the consistency of resol, and cost is not high yet.
Sun Yuzhuo etc. are at " the rubber and plastic utilization of resources " of 2006 the 6th phase 7-10 pages or leaves useless nylon-6 silk of a kind of usefulness of having gone up bewrite; With NaOH is catalyzer; The method for preparing the modification resol; Find that nylon-6 can certain graft reaction take place with resol, thereby further increased consistency.Yet because therefore the easy thermofixation of resole self, prepares the gel that modified phenolic resins is prone to cause reaction system with aforesaid method, it is lower that reaction and devolatilization temperature must be controlled, and is difficult to be committed to practical application.
USP 4; 110; 277 disclose a kind of resin modified phenol resin fiber of modified nylon, and containing mass parts in the used resol is the aliphatics nylon of 5-30%, and the method for preparing modification of nylon is that nylon and resol are used the solvent blend down through melt blending or high temperature.So just, can cause high energy consumption, solvent consumption, processing safety in the blend process to reduce, postprocessing working procedures such as increases at problem.
In a word, with the common nylon modified phenolic resin part that also comes with some shortcomings, for example; The water-absorbent of common nylon, especially nylon-6 and nylon-66 is strong, melt temperature is high, consumes solvent; The viscosity of its modified phenolic resins is higher, and these not only cause the high energy consumption of melt blending process, and cost is high; Processing safety reduces, and also can cause its modified resin that the wetting capacity of filler is reduced problems such as the electrical property reduction of matrix material.
Summary of the invention
The invention provides a kind of preparation method of long carbon chain nylon modified phenolic resins, this method reaction temperature with, energy consumption is low, a little less than the resol good toughness of preparation, the water absorbability, easy for industrialized is amplified.
A kind of preparation method of long carbon chain nylon modified phenolic resins comprises: long carbon chain nylon, phenol and an acidic catalyst are mixed, and heating makes the long carbon chain nylon dissolving; Drip formalin, stir while dripping, the dropping time is 20 minutes～2 hours; Control reaction temperature is 94～102 ℃; Reacted purifying, drying after being added dropwise to complete again 2～5 hours.
Described long carbon chain nylon is: the carbonatoms summation is no less than 16 nylon in two carbochains that in molecule, connected by amido linkage; Compare with common nylon; Long carbon chain nylon has that toughness is better, water-absorbent is low, melt temperature is lower and advantage such as solvent nature is better, and the resol of preparation has preferably toughness and than low water absorbable.
Be preferably PA-12 12, nylon-11 11, nylon-1010, nylon-610, nylon-6 12, nylon-1313, nylon-8, nylon-9; At least a in nylon-11 and the PA-12, at least a in PA-12 12, nylon-11 and the nylon-1010 more preferably.
Described long carbon chain nylon weight is preferably 1～20% of phenol weight.
Described an acidic catalyst weight is 0.1～5% of phenol weight.
Formaldehyde and phenol mol ratio are 0.75～0.85 in the described formalin.
Described formalin massfraction is 20～45%.
Said an acidic catalyst is at least a in inorganic proton acid, organic acid and the organic acid anhydride, is preferably in hydrochloric acid, sulfuric acid, phosphoric acid, Phenylsulfonic acid, sodium pyrosulfate, oxalic acid, toxilic acid, phenylformic acid, oxalic anhydride and the maleic anhydride at least a.
The present invention also provides a kind of long carbon chain nylon resin modified phenol resin, contains weight percent in the described resol and be 1～20% long carbon chain nylon, and viscosity is 30～350CP when temperature is 130 ℃.
Second-order transition temperature is roughly 35～45 ℃.
Preferably, described resol preparation method comprises: long carbon chain nylon, phenol and an acidic catalyst are mixed, and heating makes the long carbon chain nylon dissolving; Drip formalin, stir while dripping, control reaction temperature is 94～102 ℃; Reacted purifying, drying after being added dropwise to complete again 2～5 hours.
The inventive method is dissolved in long carbon chain nylon in the phenol in advance, because phenol is the fine solvent of nylon, compares with the preparation method of resol melt blending; Help saving energy and reduce the cost; Need not equipment is carried out extra transformation, reaction conditions is also comparatively gentle, helps stablizing the resol quality; Select for use acid so just to avoid, problem such as easy gel of having avoided causing with alkaline catalysts and devolatilization temperature are low for catalyzer; Select the technology of slow dropping formaldehyde for use, can be in avoiding reaction process long carbon chain nylon separate out problems such as the mixing that is caused is inhomogeneous.
Specific embodiment
Embodiment 1
400g phenol, 40g PA-12 12 and oxalic acid 3g are put in the reaction kettle of 2L, start stirring, be heated to 100 ℃, PA-12 12 will be dissolved in the middle of the phenol gradually this moment, form homogeneous solution.Then, slowly be added dropwise to the formalin (37% massfraction) (mol ratio of phenol and formaldehyde is 1: 0.8) of metering with constant pressure funnel, keeping reactor temperature is 94-100 ℃, and the dropping time is 20-30 minute.Be reflected at and proceed half a hour approximately under the reflux temperature, system will reach the phase transformation cloud point, thereby become the oyster white troubled liquor, and will be last, continue reaction 2 hours down in reflux temperature.Then, connect vacuum exhaust pipe, under constantly stirring, decompression devolatilization two hours; Vacuum tightness is 0-0.1MPa, and then, the temperature of system will slowly be elevated to 150 ℃, under this temperature, continues decompression devolatilization 1 hour; At last, discharging while hot gets PA-12 12 modified phenolic resinss.
Embodiment 2
400g phenol, 80g PA-12 12 and oxalic acid 3g are joined in the 2L reaction kettle, constantly stir, be heated to 100 ℃, PA-12 12 will be dissolved in the middle of the phenol gradually this moment, form homogeneous solution.Then, slowly be added dropwise to the formalin (37% mass parts) (mol ratio of phenol and formaldehyde is 1: 0.8) of metering with constant pressure funnel, temperature of reaction is 94-100 ℃, drips and takes 20-30 minute.Along with the carrying out of reaction, system will be passed through the phase transformation cloud point and become the oyster white troubled liquor, and will be last, under reflux temperature, continue reaction 2 hours again.Then, connect vacuum exhaust pipe, constantly stirring, decompression devolatilization 2 hours, vacuum tightness is 0-0.1MPa, and temperature will slowly be elevated to 150 ℃, continue decompression devolatilization 1 hour, and will be last, and discharging while hot gets PA-12 12 modified phenolic resinss.
Embodiment 3
400g phenol, 40g nylon-11 and oxalic acid 3g are put in the reaction kettle of 2L, constantly stir, be heated to 100 ℃, nylon-11 will be dissolved in the middle of the phenol gradually this moment, form homogeneous solution.Then, slowly be added dropwise to the formalin (37% mass parts) (mol ratio of phenol and formaldehyde is 1: 0.8) of metering with constant pressure funnel, keeping temperature is 94-100 ℃, and the dropping time is 20-30 minute.Then, be reflected under the reflux temperature and proceed half a hour, system will become the oyster white turbid solution through the phase transformation cloud point, and the time is 2 hours.Then, connect vacuum exhaust pipe, and continuous the stirring, decompression devolatilization two hours, initial vacuum tightness is 0-0.1MPa, and temperature will slowly be elevated to 150 ℃, and continue devolatilization 1 hour, and will be last, and discharging while hot gets the nylon-11 modified phenolic resins.
Embodiment 4
400g phenol, 40g nylon-1010 and oxalic acid 3g are joined in the reaction kettle of 2L, start stirring, be heated to 100 ℃,, form homogeneous solution up to dissolving fully.Then, slowly be added dropwise to the formalin (37% mass parts) (mol ratio of phenol and formaldehyde is 1: 0.8) of metering with constant pressure funnel, keeping the temperature in the reaction kettle is 94-100 ℃, the process need 20-30 of whole dropping formaldehyde minute.Afterwards, under reflux temperature, continue to react half a hour, system will be passed through the phase transformation cloud point and become the oyster white troubled liquor, and the reaction times in this stage is 2 hours.Then, connect vacuum exhaust pipe, under constantly stirring, decompression devolatilization 2 hours; The vacuum tightness of initial period is 0-0.1MPa, and the temperature of system will slowly be increased to 150 ℃, and continues decompression devolatilization 1 hour; At last, discharging while hot gets the nylon-1010 modified phenolic resins.
Reference examples
400g phenol, oxalic acid 3g are put in the reaction kettle of 2L, start stirring, be heated to 100 ℃.Then, slowly drip the formalin (37% mass parts) (mol ratio of phenol and formaldehyde is 1: 0.8) of metering with constant pressure funnel, keeping temperature is 94-100 ℃, takes about 20-30 branch.Be reflected under the reflux temperature and carry out, system will reach the phase transformation cloud point and become the oyster white troubled liquor, and the reaction times is 2 hours.Then, connect vacuum exhaust pipe, and constantly stir, decompression devolatilization two hours; Vacuum tightness is 0-0.1MPa, and then, the temperature of system will slowly be elevated to 150 ℃, under this temperature, continues decompression devolatilization 1 hour; At last, discharging while hot gets unmodified common resol.
Performance test methods
With the viscosity of above-mentioned all resol of U.S. Brookfield CAP2000 type viscosity apparatus test, operating parameters is: 130 ℃ of temperature, 10 rev/mins of rotating speeds, 1 minute time;
Test the second-order transition temperature of above-mentioned resol with the anti-DSC200F3 type DSC of holding company's production of Germany; Operating parameters is: temperature rate is 10 ℃/minute; Temperature program(me): room temperature → 130 ℃ → 0 ℃ → 100 ℃, the specific heat sudden change mid point in the secondary temperature elevation process is thought the second-order transition temperature of resol.Concrete test result is shown in subordinate list 2.
Mixture and preparation method of sample
It is even that resol, urotropine, Triple Pressed Stearic Acid, mica powder and Natural manganese dioxide are pressed the mixed shown in the subordinate list 1, in two roller mills, plastifies then, mixing 10-20 minute, and the control heating steam pressure is 0.6-0.8MPa.Then, the gained print is pulverized, sieved, obtain a kind powder; After the oven dry, join in the good steel die of preheating, under 160 ℃ of pressure with 20MPa, hot-forming 4 minutes; The demoulding, cooling, deflashing make batten, and the normal temperature held was used for performance test after 24 hours; Comprise flexural strength (GB GB/T 9341-2000) and shock strength (shock strength is by GB GB/T 1843-2008), sample is " V " type notch specimen, and concrete outcome is shown in subordinate list 2.
The basic recipe of subordinate list 1 phenolic resin composite
The salient features of subordinate list 2 phenolic resin composites
From table, can find out, all make moderate progress with the flexural strength and the shock strength of the phenolic resin composite behind the modified nylon.
Claims (4)
1. the preparation method of a long carbon chain nylon modified phenolic resins; Comprise: long carbon chain nylon, phenol and an acidic catalyst are mixed; Described long carbon chain nylon weight is 1～20% of phenol weight, and long carbon chain nylon is for wherein being no less than 16 by carbonatoms summation in two carbochains of amido linkage connection; Described an acidic catalyst weight is 0.1～5% of phenol weight; Heating makes the long carbon chain nylon dissolving, drips formalin, and the formaldehyde in the described formalin and the mol ratio of phenol are 0.75～0.85; Stir while dripping, control reaction temperature is 94～102 ℃, reacted again after being added dropwise to complete 2～5 hours, and purifying, drying obtains the long carbon chain nylon modified phenolic resins; Wherein, in long carbon chain nylon modified phenolic resins total amount, wherein contain weight percent and be 1～20% long carbon chain nylon.
2. preparation method as claimed in claim 1; It is characterized in that; Described long carbon chain nylon is PA-12 12, nylon-11 11, nylon-1010, nylon-610, nylon-6 12, nylon-1313, nylon-8, nylon-9, and is at least a in nylon-11 and the PA-12.
3. preparation method as claimed in claim 1 is characterized in that, said formalin massfraction is 20%～45%.
4. preparation method as claimed in claim 1 is characterized in that, said an acidic catalyst is at least a in hydrochloric acid, sulfuric acid, phosphoric acid, Phenylsulfonic acid, sodium pyrosulfate, oxalic acid, toxilic acid, phenylformic acid, oxalic anhydride, maleic anhydride and the zinc acetate.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103897416B (en) * | 2014-03-26 | 2016-05-18 | 浙江嘉民塑胶有限公司 | A kind of phenolaldehyde moulding compound and preparation method thereof |
| CN106947055B (en) * | 2017-04-01 | 2020-08-18 | 山东益丰生化环保股份有限公司 | High-refraction resin and preparation method thereof |
| CN109251289B (en) * | 2018-08-13 | 2021-05-11 | 河南工业大学 | Preparation method of phenolic resin with heat resistance and toughness |
| CN113004480A (en) * | 2021-02-26 | 2021-06-22 | 禹城京都新材料科技有限公司 | Preparation method of toughened thermosetting liquid phenolic resin |
| CN113463396A (en) * | 2021-07-01 | 2021-10-01 | 黑龙江弘宇短纤维新材料股份有限公司 | Aramid short fiber for nylon resin product and preparation method thereof |
| CN115785360B (en) * | 2023-02-02 | 2023-05-16 | 山东诚汇新材料有限公司 | Low-abrasion phenolic resin with high strength and high toughness and synthesis process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4110277A (en) * | 1971-06-01 | 1978-08-29 | The Carborundum Company | Nylon modified phenolic resin fibers |
| CN101709516A (en) * | 2009-11-26 | 2010-05-19 | 陕西师范大学 | Method for preparing toughening agent modified phenolic fiber |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4110277A (en) * | 1971-06-01 | 1978-08-29 | The Carborundum Company | Nylon modified phenolic resin fibers |
| CN101709516A (en) * | 2009-11-26 | 2010-05-19 | 陕西师范大学 | Method for preparing toughening agent modified phenolic fiber |
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Denomination of invention: Long carbon chain nylon modified phenolic resin and preparation method thereof Effective date of registration: 20150317 Granted publication date: 20121010 Pledgee: The Agricultural Bank of Jiaxing branch of Limited by Share Ltd. China garshin Pledgor: ZHEJIANG JIAMIN PLASTIC CO.,LTD. Registration number: 2015990000198 |
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Date of cancellation: 20210714 Granted publication date: 20121010 Pledgee: The Agricultural Bank of Jiaxing branch of Limited by Share Ltd. China garshin Pledgor: ZHEJIANG JIAMIN PLASTIC Co.,Ltd. Registration number: 2015990000198 |
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Effective date of registration: 20221221 Address after: No. 999, Ruibo Avenue, Wangdian Town, Xiuzhou District, Jiaxing City, Zhejiang Province, 314000 Patentee after: ZHEJIANG JIAMIN NEW MATERIALS Co.,Ltd. Address before: Jiaxing City, Zhejiang province 314027 Wang Zhen Longyuan road construction Xiuzhou District No. 377 Patentee before: ZHEJIANG JIAMIN PLASTIC CO.,LTD. |