CN105732924A - Preparation method of boron modified phenolic resins - Google Patents
Preparation method of boron modified phenolic resins Download PDFInfo
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- CN105732924A CN105732924A CN201410765934.4A CN201410765934A CN105732924A CN 105732924 A CN105732924 A CN 105732924A CN 201410765934 A CN201410765934 A CN 201410765934A CN 105732924 A CN105732924 A CN 105732924A
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Abstract
The invention relates to a preparation method of boron modified phenolic resins, which includes the steps of: (1) preparing raw materials according to the following components, by weight, 1000 parts of phenol, 480-500 parts of formaldehyde, 10-20 parts of a catalyst, and 300-400 parts of a boric acid; (2) putting the phenol and the formaldehyde in a reaction kettle, controlling the temperature at 50 DEG C and adding half of the catalyst, and then reacting for 1 hour at a temperature of 63 DEG C to 67 DEG C; (3) smoothly heating the material to a temperature of 90 DEG C, and adding 1/10 of the boric acid; (4) maintaining the material temperature between 90 DEG C and 100 DEG C, and finishing adding the residual boric acid in 0.5 hour; (5) adding the residual catalyst in mixing components; (6) regulating and controlling a medium temperature, making the material temperature rise to 110 DEG C-120 DEG C in 0.5 hour, and carrying out constant temperature reaction for 2 hours; and (7) after the dehydration reaches a theoretical value, taking samples and measuring gel time, and preparing and obtaining the boron modified phenolic resins. Compared with the prior art, the preparation method of the boron modified phenolic resins has the advantages of stable reaction, strong controllability and high carbon yield of the resins.
Description
Technical field
The preparation method that the present invention relates to a kind of phenol-formaldehyde resin modified, the preparation method especially relating to a kind of boron modified phenolic resin, it is possible in field extensive uses such as Aero-Space, military project and brake material, electrical carbon material, wear resistance material, refractory materials.
Background technology
Currently mainly there are three kinds by the method for boron compound phenol-formaldehyde resin modified.1. boron compound is introduced in the synthesis latter stage of phenolic resin or use procedure early stage, boron compound is made first to enter in phenolic resin with physical admixture, then react at hot setting stage boron compound and phenolic resin, form part B-O key, thus improve phenolic resin performance, fail due to boron element and phenolic resin fully reacts, it does not have fundamentally change combination property.2. first boracic phenyl ester is generated with boron compound and phenols reaction, then boron modified phenolic resin is generated with formaldehyde reaction again, there is a lot of weak point in this method: has a large amount of phenol to run off with reaction water when a esterification time length, temperature height, condensation, cause mol ratio uncontrollable.B: after adding formaldehyde, thermal discharge is big, and reaction temperature is high, controls difficulty, it is impossible to industrialization.C: esterification is complicated, is difficult to generate desirable triphenylmethyl methacrylate, a lot of derivatization reaction occurs, creates a lot of complicated little molecule, late stage process is produced uncontrollable factor.3. first make phenol and formalin water generation reaction poplar alcohol in the basic conditions, then prepare boron modified phenolic resin with boron compound reaction.This method also has disadvantages that: a response time is long, and it is more difficult that temperature controls.The waste water that b liquid formaldehyde produces is many, and unfavorable environmental protection, dewatering time is long, lowers efficiency.C: the quantity of bad grasp saligenin generation and speed, is also unfavorable for controlling the ripe degree of resinification, it is easy to go out waste material and cohesion.
The quality of boron modified phenolic resin thermostability, mainly sees the quantity that B-O key generates, because B-O bond energy is much larger than the C-C bond energy being primarily present in phenolic resin.How to improve the quantity of B-O key, be the key improving boron modified phenolic resin performance.
Chinese patent CN101693821A discloses boron modified phenolic resin binder for refractory materials, phenol resin solution adds many sodium borate, can being eight sodium borate and/or ten sodium borate, the addition of many sodium borate be the 0.2～3% of phenolic resin, and unit is mass percent.This bonding agent has higher carbon yield, relatively low viscosity, also improves thermostability and non-oxidizability.This patent is interpolation boron compound in synthetic B rank phenolic resin, and only in resin curing process, boron compound could participate in reaction, and boron compound utilization rate is low, and addition is about 5%.Although the method increasing the carbon yield of phenolic resin, heat resistance, but the resin carbon yield of synthesis also can only achieve 60～65%.Present invention process, employing is phenol, formaldehyde, boron compound synchronous reaction, and the addition of boron compound can reach 20% (mass ratio), and boron element can effectively participate in reaction, substitutes the H in hydroxyl, forms B-O key.The phenolic resin of final synthesis has significantly high carbon yield (70～75%) and heat resistance.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and preparation method that boron modified phenolic resin that a kind of reacting balance, controllability B-O bond number amount strong, that formed is many is provided.
The purpose of the present invention can be achieved through the following technical solutions:
The preparation method of a kind of boron modified phenolic resin, adopts following steps:
(1) get the raw materials ready according to following components and weight portion content: phenol 1000, formaldehyde 480～500, catalyst 10～20, boric acid 300～400；
(2) phenol, formaldehyde are put in reactor, control temperature 50 C and add half catalyst, then react 1h in 63-67 DEG C；
(3) temperature of charge is steadily risen to 90 DEG C, add 1/10th boric acid；
(4) keep temperature of charge 90-100 DEG C, in 0.5h, add remaining boric acid；
(5) in blending ingredients, remaining catalyst is added；
(6) regulation and control medium temperature, makes to rise to 110-120 DEG C in temperature of charge 0.5h, isothermal reaction 2h, the refractive index of sampling detection material, as reached requirement, then carries out decompression dehydration.
(7) dehydration reach a certain amount of after, gel time is surveyed in sampling, at 100s ± 10s/180 DEG C, outward appearance yellow bright transparent time discharging, prepare boron modified phenolic resin.
Preferably, formaldehyde is the solid formaldehyde of 96wt%, and remainder is mostly moisture content, does not affect resins synthesis, and catalyst is sodium hydroxide.
In step (6), the refractive index of material is 1.1570～1.1590.
In step (7), dehydrating amount is 50wt%.
Compared with prior art, the present invention adopts phenol, solid formaldehyde to react in the basic conditions, generating portion saligenin, adds after boric acid, boric acid and saligenin grafting；Esterification occurs between boric acid and phenol, and formaldehyde again and reacts between phenyl ester；In course of reaction, also create part phenolic resin, boron element and phenolic resin key even.The above-mentioned utilization rate waiting combined reaction can improve boron element, has the advantage that
1. reacting balance, controllability is strong, and catalyst is sodium hydroxide, and activity is high, and gradation adds, it is possible to prevent reaction too fast.
2. generation a small amount of reaction water, relatively environmental protection.
3. generating the cycle short, efficiency is high, can quantify to produce, save the energy and unit cost.After technological process terminates, end product is solid thermosetting phenolic resin.
4. fully participate in reaction due to boron element, the B-O bond number amount of formation is many, has higher thermostability and carbon yield, adds boric acid with batch process, can effectively stablize reaction temperature；Between 90～100 DEG C, reaction contributes to acid esterification and saligenin grafting；110～120 DEG C is reaction peak, is conducive to boron element and phenolic hydroxyl group and methylene reaction.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
The preparation method of a kind of boron modified phenolic resin, adopts following steps:
(1) get the raw materials ready according to following components and content: the solid formaldehyde 480g of phenol 1000g, 96wt%, catalyst sodium hydroxide 10g, boric acid 300g；
(2) phenol, formaldehyde are put in reactor, control temperature 50 C and add half catalyst, then react 1h in 63 DEG C；
(3) temperature of charge is steadily risen to 90 DEG C, add 1/10th boric acid；
(4) keep temperature of charge 90 DEG C, in 0.5h, add remaining boric acid；
(5) in blending ingredients, remaining catalyst is added；
(6) regulation and control medium temperature, makes to rise in temperature of charge 0.5h 120 DEG C, isothermal reaction 2h, and the refractive index of sampling detection material is 1.1575, carries out decompression dehydration.
(7), after dehydration reaches 50g, sampling is surveyed gel time and is 98s/180 DEG C, outward appearance yellow bright transparent time discharging, prepare boron modified phenolic resin.
Embodiment 2
The preparation method of a kind of boron modified phenolic resin, adopts following steps:
(1) get the raw materials ready according to following components and content: the solid formaldehyde 486g of phenol 1000g, 96wt%, catalyst sodium hydroxide 15g, boric acid 360g；
(2) phenol, formaldehyde are put in reactor, control temperature 50 C and add half catalyst, then react 1h in 63 DEG C；
(3) temperature of charge is steadily risen to 90 DEG C, add 1/10th boric acid；
(4) keep temperature of charge 90 DEG C, in 0.5h, add remaining boric acid；
(5) in blending ingredients, remaining catalyst is added；
(6) regulation and control medium temperature, makes to rise in temperature of charge 0.5h 110 DEG C, isothermal reaction 2h, and the refractive index of sampling detection material is 1.1579, carries out decompression dehydration.
(7), after dehydration reaches 50g, sampling is surveyed gel time and is 105s/180 DEG C, outward appearance yellow bright transparent time discharging, prepare boron modified phenolic resin.
Embodiment 3
The preparation method of a kind of boron modified phenolic resin, adopts following steps:
(1) get the raw materials ready according to following components and content: the solid formaldehyde 500g of phenol 1000g, 96wt%, catalyst sodium hydroxide 20g, boric acid 400g；
(2) phenol, formaldehyde are put in reactor, control temperature 50 C and add half catalyst, then react 1h in 63 DEG C；
(3) temperature of charge is steadily risen to 90 DEG C, add 1/10th boric acid；
(4) keep temperature of charge 90 DEG C, in 0.5h, add remaining boric acid；
(5) in blending ingredients, remaining catalyst is added；
(6) regulation and control medium temperature, makes to rise in temperature of charge 0.5h 120 DEG C, isothermal reaction 2h, and the refractive index of sampling detection material is 1.1587, carries out decompression dehydration.
(7), after dehydration reaches 50g, sampling is surveyed gel time and is 108s/180 DEG C, outward appearance yellow bright transparent time discharging, prepare boron modified phenolic resin.
Comparative example
The preparation method of a kind of boron modified phenolic resin, adopts following steps:
(1) get the raw materials ready according to following components and content: the solid formaldehyde 500g of phenol 1000g, 96wt%, catalyst sodium hydroxide 20g；
(2) phenol, formaldehyde are put in reactor, control temperature 50 C and add half catalyst, then react 1h in 63 DEG C；
(3) 0.5h is reacted after temperature of charge steadily being risen to 90 DEG C；
(4) in blending ingredients, remaining catalyst is added；
(5) regulation and control medium temperature, makes to rise in temperature of charge 0.5h 120 DEG C, carries out decompression dehydration after isothermal reaction 2h.
(6) after dehydration reaches 50g, discharging, prepare boron modified phenolic resin.
| Embodiment | Carbon yield (%) | Gel time (sec)/180 DEG C | Free phenol (%) |
| Embodiment 1 | 72 | 100 | 4.5 |
| Embodiment 2 | 72 | 106 | 4.5 |
| Embodiment 3 | 74 | 108 | 4.2 |
| Comparative example | 52 | 106 | 4.8 |
From embodiment, the carbon yield of resin detection is it can be seen that boron modified phenolic resin carbon yield prepared by the present invention exceeds about 20% than the carbon yield without boron compound.But the height of carbon yield directly affects the thermostability of resin, so boron modified phenolic resin carbon yield prepared by the present invention is high, heat-resist.
Claims (5)
1. the preparation method of a boron modified phenolic resin, it is characterised in that the method adopts following steps:
(1) get the raw materials ready according to following components and weight portion content: phenol 1000, formaldehyde 480～500, catalyst 10～20, boric acid 300～400；
(2) phenol, formaldehyde are put in reactor, control temperature 50 C and add half catalyst, then react 1h in 63-67 DEG C；
(3) temperature of charge is steadily risen to 90 DEG C, add 1/10th boric acid；
(4) keep temperature of charge 90-100 DEG C, in 0.5h, add remaining boric acid；
(5) in blending ingredients, remaining catalyst is added；
(6) regulation and control medium temperature, makes to rise to 110-120 DEG C in temperature of charge 0.5h, isothermal reaction 2h, the refractive index of sampling detection material, as reached requirement, then carries out decompression dehydration.
(7) dehydration reach a certain amount of after, gel time is surveyed in sampling, at 100s ± 10s/180 DEG C, outward appearance yellow bright transparent time discharging, prepare boron modified phenolic resin.
2. the preparation method of a kind of boron modified phenolic resin according to claim 1, it is characterised in that described formaldehyde is the solid formaldehyde of 96wt%.
3. the preparation method of a kind of boron modified phenolic resin according to claim 1, it is characterised in that described catalyst is sodium hydroxide.
4. the preparation method of a kind of boron modified phenolic resin according to claim 1, it is characterised in that in step (6), the refractive index of material is 1.1570～1.1590.
5. the preparation method of a kind of boron modified phenolic resin according to claim 1, it is characterised in that in step (7), dehydrating amount is 50wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206636A (en) * | 2018-07-27 | 2019-01-15 | 西北工业大学深圳研究院 | One kind hollow beads containing boron bakelite resin and preparation method thereof |
| CN110102704A (en) * | 2019-05-28 | 2019-08-09 | 沙县宏盛塑料有限公司 | A kind of modification phenolic resin-based precoated sand and preparation method thereof |
| CN111471149A (en) * | 2020-05-19 | 2020-07-31 | 安徽凯沃科技有限公司 | Silicon modified phenolic resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531769A (en) * | 2009-04-17 | 2009-09-16 | 上海应用技术学院 | Method for preparing high temperature resistance phenolic aldehyde foam insulating composite material |
| CN102604020A (en) * | 2012-03-14 | 2012-07-25 | 沙县宏盛塑料有限公司 | Boron modified phenolic resin and preparation method thereof |
| CN102746479A (en) * | 2011-04-19 | 2012-10-24 | 襄樊学院 | Preparation method of boron-containing phenolic resin for friction materials |
-
2014
- 2014-12-11 CN CN201410765934.4A patent/CN105732924A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531769A (en) * | 2009-04-17 | 2009-09-16 | 上海应用技术学院 | Method for preparing high temperature resistance phenolic aldehyde foam insulating composite material |
| CN102746479A (en) * | 2011-04-19 | 2012-10-24 | 襄樊学院 | Preparation method of boron-containing phenolic resin for friction materials |
| CN102604020A (en) * | 2012-03-14 | 2012-07-25 | 沙县宏盛塑料有限公司 | Boron modified phenolic resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 霍靓靓等: "硼改性酚醛树脂的合成", 《河南科学》 * |
| 黄发荣等: "《酚醛树脂及其应用》", 13 January 2003 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206636A (en) * | 2018-07-27 | 2019-01-15 | 西北工业大学深圳研究院 | One kind hollow beads containing boron bakelite resin and preparation method thereof |
| CN109206636B (en) * | 2018-07-27 | 2021-05-28 | 西北工业大学深圳研究院 | Boron-containing phenolic resin hollow microsphere and preparation method thereof |
| CN110102704A (en) * | 2019-05-28 | 2019-08-09 | 沙县宏盛塑料有限公司 | A kind of modification phenolic resin-based precoated sand and preparation method thereof |
| CN110102704B (en) * | 2019-05-28 | 2020-12-18 | 沙县宏盛塑料有限公司 | Modified phenolic resin-based precoated sand and preparation method thereof |
| CN111471149A (en) * | 2020-05-19 | 2020-07-31 | 安徽凯沃科技有限公司 | Silicon modified phenolic resin and preparation method thereof |
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Effective date of registration: 20170914 Address after: 230601 Anhui province Bengbu Kaiyuan Avenue estuary Industrial Park Huaishang District No. 38 Mo Applicant after: Anhui composite material science and Technology Co Ltd Address before: 201306 No. 47 A0201 neighborhood, Lingang hi tech industrialization base, Shanghai, Pudong New Area Applicant before: Shanghai Advanced Engineering Materials Co., Ltd. |
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