CN109384897A - A method of enhancing biomass phenolic foam heat resistance - Google Patents

Abstract

The present invention relates to a kind of preparation methods of biomass phenolic foam heat resistance.Biomass material containing phenolic hydroxyl group carries out acid esterification with phenol and boric acid in acid condition and reacts, the esterification products and paraformaldehyde carry out addition polycondensation under alkaline condition, it is eventually adding and ties up aldehyde agent, obtain boron modification biomass foamed phenolic resin, free phenol and free aldehyde significantly reduce.The resin and blowing promotor are blended in foamed solidification under certain temperature, prepare the good biomass phenolic foam of heat resistance, and 469.6 DEG C of thermal decomposition temperature, most fast 548.5 DEG C of temperature of mass loss rate, 800 DEG C of carbon residues 77.88%.What phenol formaldehyde foam had not only been widened in the research and development of the foam uses field, but also China's biomass resource cheap and easy to get provides a high added value approach, while reducing phenol formaldehyde foam industry to the dependence of petrochemical material phenol.

Description

A method of enhancing biomass phenolic foam heat resistance

Technical field

The present invention relates to a kind of preparation methods for improving biomass phenolic foam heat resistance, belong to Material Field.It is prepared Foamed heat-resistance be improved, that is, reduce costs and protect environment, be applicable to chemical company and power-plant flue gas pipe The industrial circles such as road have in the case where country is gradually stringent to thermal insulation material flame-retardancy requirements from the fire-retardant product city Field has good prospects.

Background technique

In recent years, with the fast development of the industries such as building, petrochemical industry, ship, light, fire prevention, low toxicity material by Gradually it is taken seriously.In common heat-insulating foam material, the phenolic foam advantage incomparable with other foamed plastics And it is widely applied.According to industry specialists according to the analysis, phenolic foam will be in central air conditioner system, light thermal-insulation coloured silk steel Fully develop talents in the fields such as plate, house heat-barrier material, petrochemical pipe.Wherein petrochemical industry is infrastructural industry for the national economy, is needed A large amount of various pipeline supports play series of process process, energy saving in order to meet production requirement, improve working conditions, work Skill pipeline requires to be thermally insulated.The Conventional insulation that petrochemical industry uses such as keeps the temperature asbestos, perlite and gathers Urethane foam etc. weatherability, it is corrosion-resistant, environmentally friendly, in terms of there is such or such defect mostly.Especially preventing fires It is required that stringent production division, such as natural gas liquefaction station, low boiling point Storage Tanks Combustible Liquid, phenol formaldehyde foam is good thermal insulating material Material.In addition, petrochemical industry carries out safety equipment maintenance every year, the thermal insulation material total amount needed is up to more than 20 ten thousand steres, often The thermal insulation material that year grassroot project uses reaches more than 15 ten thousand steres.Whole industry thermal insulation material demand is larger, but phenolic aldehyde steeps Foam can be used for a long time at 150 DEG C or less, and 200 DEG C begin to degrade, and chemical company's jet chimney temperature or reaction medium stream Temperature is generally greater than 150 DEG C, and power-plant flue gas pipe is also relatively high to temperature, for energy saving, it is necessary to carry out to these pipelines Heat preservation, therefore the phenolic foam products for researching and developing heat resistance are of great significance.

Phenol formaldehyde foam has foamed phenolic resin and blowing promotor to be blended in foamed solidification under certain temperature to form, therefore studies phenol The heat resistance of aldehyde foam is mainly exactly to study the heat resistance of foamed phenolic resin.Conventional unmodified phenolic resin brittleness is big, toughness The disadvantages of difference and poor heat resistance, limits the development of its high performance material.Therefore, phenolic resin is modified, it is heat-resisting improves its Property and toughness be phenolic resin material development direction, boron modified phenolic resin is current most successful phenolic resin modified kind One of.It is solid boron modified phenolic resin that boron element, which is introduced the more research of phenolic resin, for friction material, moulding compound and Laminated material etc., as Wang Lei (2009, high temperature resistant boron phenolic PRODUCTION TRAITS) first step first prepares phenyl-borate, then and paraformaldehyde Boron modified phenolic resin is prepared, is dissolved in ethyl alcohol for composite laminate.Temperature is more than only weightlessness 27.7% after 450 DEG C.Qiu Jun (2007, Tongji University's journal (natural science edition)) first generate phenyl-borate with phenol solid and acid reaction, and toluene is as molten Agent is prepared for the resin solid of chartreuse using obtained intermediate phenyl-borate and polyformaldehyde reaction.High boron content Weight-loss ratio of the resin at 1200 DEG C is only 34.7%, and carbon yield is up to 65.3%；It can be used for the matrix resin of ablation resistant material. Zhang Min (2004, synthesis chemistry) is reacted using first phenol with formaldehyde, and the saligenin and acid reaction of generation are obtained by twice dehydration To the thermosetting phenolic resin of solid, ethyl alcohol, 500 DEG C of weightlessness 15%, comprehensive performance domestic military use product before reaching are dissolved in Index.Wang Xiaowei (2013, Xiamen University's journal (natural science edition)) is using boric acid, phenol, liquid formaldehyde as raw material, using two steps Method prepares solid boron modified phenolic resin, can be used as the matrix resin of high-temperature brake friction material.

In phenol formaldehyde foam field, yellow sword equal clearly (2007, glass reinforced plastic/composite material) makees catalyst with sodium hydrate aqueous solution Phenol formaldehyde (PF) carries out addition polycondensation, and the reaction later period is neutralized with boric acid, synthesizes foamable boron modification foamed phenolic resin, and prepare Boron modification phenol formaldehyde foam out, the foam maximum operation (service) temperature are 200 DEG C.Yellow sword grade clearly (2013, Shanghai Institute Of Technology's journal (natural science edition)) with alkaline silica sol make catalyst and boric acid makees the method for neutralizer and synthesized foamed phenolic resin, and make It is up to 200 DEG C for borosilicate modified phenolic foam, the use environment temperature of foam.It is prepared by Pan Wen (2016, technical research) During phenol formaldehyde foam, foamed phenolic resin, boric acid and blowing promotor high speed are blended, pour into grinding tool foaming, the results showed that boron Element improves the heat resistance of foam, and 950 DEG C of carbon yield is 67.2%.Wang Bin (2013, Chinese material progress) is using certainly The resol of system, mould hair is blended with phenolic aldehyde tiny balloon and diboron trioxide, and boron modification is conducive to the height of phenol formaldehyde foam Temperature stability, when diboron trioxide content is mass fraction 7%, the high temperature resistance of phenol formaldehyde foam is optimal, weightlessness 10% When thermal decomposition temperature be 447 DEG C.Current document is by boric acid in Foamex in terms of the heat-resisting Journal of Sex Research of phenol formaldehyde foam Later period addition is reacted, neutralizer is on the one hand used as, on the other hand inadequate as heat-resisting element and resin reaction degree, boron element is not Exist completely in the form of boron oxygen key.Boron element is just introduced in initial reaction stage, reacts boron sufficiently with phenolic hydroxy group raw material, is obtained resistance to Hot higher phenol formaldehyde foam, is suitable for some special dimensions, and the research of this respect has not been reported.

Summary of the invention

With country promote conservation-minded society development, not only building thermal insulation material market is in the ascendant, chemical company and The industries such as power plant also pay attention to the energy-saving and emission-reduction of enterprise, reduce entreprise cost.The present invention relates to one kind to be suitable for business unit's pipeline The heat resistance biomass phenolic foam thermal insulation material of heat preservation.

A method of enhancing biomass phenolic foam heat resistance.This method is with the biomass material, boric acid, benzene of hydroxyl Phenol and paraformaldehyde are primary raw material, which is characterized in that this method includes three steps: the first step is the synthesis of boric acid phenolic ester. Acidic catalyst is added in the phenol of thawing, blending and stirring is uniform, add hydroxyl biomass and its derivative products and Boric acid is warming up to 110-140 DEG C, isothermal reaction 2-3h, separates the water that reaction generates using water segregator, prepares borate.Second Portion is the preparation of boron modification biomass foamed phenolic resin.The first step after the reaction was completed, is cooled to 55-65 DEG C, and base catalysis is added Paraformaldehyde is added in agent pH value to 8.5-9.5, substep, in 70-75 DEG C of reaction 1-1.5h, is then warming up to 85-90 reaction 0.5- Aldehyde agent, cooling discharge are tied up in 1h, addition.Third step is the preparation of phenol formaldehyde foam.By homemade boron modification biomass foamable phenolic tree Rouge is blended with blowing promotor, at a certain temperature foamed solidification, obtains the good biomass phenolic foam plastics of heat resistance.

The biomass material of phenolic hydroxy group used include two classes, one kind be directly utilize biomass resource it is effective at Point, such as lignin, anacardol, tannin, another kind of is using biomass liquefying product and biomass pyrolysis product, such as timber liquid Change product, pyrolysis oil and tar etc.；

The acid esterification catalyst can be keggin heteropoly acid, such as phosphato-molybdic heteropolyacid, can also be miscellaneous more with Dawson Acid, such as molybdenum vanadium phospha polyacid；

The boric acid accounts for the 3-7% of the sum of biomass material and phenol quality；It is 110-140 DEG C of esterification reaction temperature, permanent Temperature reaction 2-3h,

The phenolic aldehyde molar ratio is 1: 1.5-1: 2.0；

The biomass material of the phenolic hydroxy group accounts for the 10-15% of phenol quality；

The boric acid accounts for the 3-7% of phenol and phenolic hydroxy group biomass material gross mass；

It is cooled to 55-65 DEG C after the esterification, base catalyst tune pH value is added to 8.5-9.5, poly first is added in substep Then aldehyde is warming up to 85-90 reaction 0.5-1h, paraformaldehyde divides 3-4 step to be added, in 70-75 in 70-75 DEG C of reaction 1-1.5h DEG C reaction 1-1.5h, be then warming up to 85-90 DEG C of reaction 2-3h；

The base catalyst is sodium (potassium) base alkali or sodium (potassium) base alkalinity weak base salt, such as sodium hydroxide (potassium), bicarbonate Sodium (potassium), sodium carbonate (potassium)；

The aldehyde agent of tiing up is urea or melamine；

The curing agent is phosphoric acid, p-methyl benzenesulfonic acid, dithyl sulfate and water, mass ratio 30-20: 50-70: 20- 30:40-50；

The foaming formulation: boron modification biomass phenolic resin: foaming agent: curing agent: surfactant (mass ratio) 100∶6-10∶15-30∶2-5。

The utility model has the advantages that

It participates in reacting using boric acid as one of reactant, rather than is added in the later period for preparing resin, the thermal decomposition of foam 469.6 DEG C of temperature, most fast 548.5 DEG C of temperature of mass loss rate, 800 DEG C of carbon residues 77.88% (air atmosphere).Foam it is resistance to Hot increase rate is obvious, has widened the application field of phenol formaldehyde foam.

The use of phenolic hydroxy group biomass material reduces the cost of phenol formaldehyde foam, provides a height for biomass material Added value approach.

Embodiment 1

This method includes three steps: the first step is the synthesis of boric acid phenolic ester.It is miscellaneous that phosphorus molybdenum is added in whole phenol of thawing Polyacid, blending and stirring is uniform, adds lignin (the 10% of phenol quality) and boric acid (phenol and phenolic hydroxy group biomass material The 3% of gross mass), 110 DEG C, isothermal reaction 2h are warming up to, the water that reaction generates is separated using water segregator, prepares boric acid phenolic ester. Second step is the preparation of boron modification biomass foamed phenolic resin.The first step after the reaction was completed, is cooled to 55 DEG C, and hydroxide is added Sodium pH value divides 3-4 addition paraformaldehyde (phenolic aldehyde molar ratio is 1: 1.7), in 70 DEG C of reaction 1h, is then warming up to 85 to 8.5 DEG C reaction 2h, be added urea, cooling discharge.Third step is the preparation of phenol formaldehyde foam.Homemade boron modification biomass phenolic resin: Foaming agent: curing agent: solidifying 15min at 100: 6: 15: 2,70 DEG C of surfactant (mass ratio), obtains modified foam.

Embodiment 2

This method includes three steps: the first step is the synthesis of boric acid phenolic ester.Molybdenum vanadium phosphorus is added in whole phenol of thawing Heteropoly acid, blending and stirring is uniform, adds cashew nut shell oil (the 12% of phenol quality) and boric acid (phenol and phenolic hydroxy group biomass The 5% of total mass of raw material), 120 DEG C, isothermal reaction 2.5h are warming up to, the water that reaction generates is separated using water segregator, prepares boric acid Phenolic ester.Second step is the preparation of boron modification biomass foamed phenolic resin.The first step after the reaction was completed, is cooled to 55 DEG C, is added Potassium hydroxide pH value is divided 3-4 addition paraformaldehyde (phenolic aldehyde molar ratio is 1: 1.7), in 70 DEG C of reaction 1h, is then risen to 8.5 Melamine, cooling discharge is added to 85 DEG C of reaction 2h in temperature.Third step is the preparation of phenol formaldehyde foam.Homemade boron modification biology Matter phenolic resin: foaming agent: curing agent: solidify 15min at 100: 8: 20: 2,70 DEG C of surfactant (mass ratio), changed Sex vesicle foam.

Embodiment 3

This method includes three steps: the first step is the synthesis of boric acid phenolic ester.It is miscellaneous that phosphorus molybdenum is added in whole phenol of thawing Polyacid, blending and stirring is uniform, and adding tannin (the 14% of phenol quality) and boric acid, (phenol and phenolic hydroxy group biomass material are total The 6% of quality), 130 DEG C, isothermal reaction 2.5h are warming up to, the water that reaction generates is separated using water segregator, prepares boric acid phenolic ester. Second step is the preparation of boron modification biomass foamed phenolic resin.The first step after the reaction was completed, is cooled to 55 DEG C, and sodium carbonate is added PH value divides 3-4 addition paraformaldehyde (phenolic aldehyde molar ratio is 1: 1.8), in 72 DEG C of reaction 1h, is then warming up to 85 DEG C to 9.0 2h is reacted, urea, cooling discharge is added.Third step is the preparation of phenol formaldehyde foam.Homemade boron modification biomass phenolic resin: hair Infusion: curing agent: solidifying 15min at 100: 8: 20: 2,70 DEG C of surfactant (mass ratio), obtains modified foam.

Embodiment 4

This method includes three steps: the first step is the synthesis of boric acid phenolic ester.Molybdenum vanadium phosphorus is added in whole phenol of thawing Heteropoly acid, blending and stirring is uniform, adds Wood liquefied product (the 15% of phenol quality) and boric acid (phenol and phenolic hydroxy group life The 7% of raw material of substance gross mass), 140 DEG C, isothermal reaction 2.5h are warming up to, separates the water that reaction generates, preparation using water segregator Boric acid phenolic ester.Second step is the preparation of boron modification biomass foamed phenolic resin.The first step after the reaction was completed, is cooled to 60 DEG C, Potassium carbonate pH value is added to 9.5, divides 3-4 addition paraformaldehyde (phenolic aldehyde molar ratio is 1: 1.9), in 72 DEG C of reaction 1.5h, so After be warming up to 90 DEG C of reaction 1.5h, melamine, cooling discharge is added.Third step is the preparation of phenol formaldehyde foam.Homemade boron changes Property biomass phenolic resin: foaming agent: curing agent: surfactant (mass ratio) 100: 8: 25: 3 solidifies 18min at 75 DEG C, Obtain modified foam.

Embodiment 5

This method includes three steps: the first step is the synthesis of boric acid phenolic ester.Molybdenum vanadium phosphorus is added in whole phenol of thawing Heteropoly acid, blending and stirring is uniform, adds pyrolysis oil (the 12% of phenol quality) and boric acid (phenol and phenolic hydroxy group biomass original Expect the 6% of gross mass), 135 DEG C, isothermal reaction 3h are warming up to, the water that reaction generates is separated using water segregator, prepares boric acid phenol Ester.Second step is the preparation of boron modification biomass foamed phenolic resin.The first step after the reaction was completed, is cooled to 60 DEG C, and carbon is added Sour hydrogen sodium pH value is divided 3-4 addition paraformaldehyde (phenolic aldehyde molar ratio is 1: 1.8), in 72 DEG C of reaction 1.5h, is then risen to 9.0 Urea, cooling discharge is added to 90 DEG C of reaction 1.5h in temperature.Third step is the preparation of phenol formaldehyde foam.Homemade boron modification biomass Phenolic resin: foaming agent: curing agent: solidify 18min at 100: 10: 25: 3,75 DEG C of surfactant (mass ratio), be modified Foam.

Embodiment 6

This method includes three steps: the first step is the synthesis of boric acid phenolic ester.It is miscellaneous that phosphorus molybdenum is added in whole phenol of thawing Polyacid, blending and stirring is uniform, and adding tar (the 10% of phenol quality) and boric acid, (phenol and phenolic hydroxy group biomass material are total The 5% of quality), 120 DEG C, isothermal reaction 3h are warming up to, the water that reaction generates is separated using water segregator, prepares boric acid phenolic ester.The Two steps are the preparation of boron modification biomass foamed phenolic resin.The first step after the reaction was completed, is cooled to 60 DEG C, and saleratus is added PH value divides 3-4 addition paraformaldehyde (phenolic aldehyde molar ratio is 1: 1.8), in 72 DEG C of reaction 2h, is then warming up to 90 DEG C to 9.0 1.5h is reacted, melamine, cooling discharge is added.Third step is the preparation of phenol formaldehyde foam.Homemade boron modification biomass phenolic aldehyde Portions of resin foaming agent: curing agent: solidifying 20min at 100: 8: 28: 3,75 DEG C of surfactant (mass ratio), obtains modified foam.

Comparative example

This method includes two steps: the first step is the preparation of the preparation of biomass foamed phenolic resin.The whole of thawing Phosphato-molybdic heteropolyacid is added in phenol, blending and stirring is uniform, adds tar (the 10% of phenol quality), is warming up to 120 DEG C, constant temperature Be cooled to 60 DEG C after reaction 3h, saleratus pH value be added to 9.0, divide 3-4 addition paraformaldehyde (phenolic aldehyde molar ratio is 1: 1.8), in 72 DEG C of reaction 2h, 90 DEG C of reaction 1.5h are then warming up to, melamine, cooling discharge is added.Second step is phenolic aldehyde bubble The preparation of foam.Homemade biomass phenolic resin: foaming agent: curing agent: surfactant (mass ratio) 100: 10: 30: 3,75 Solidify 20min at DEG C, obtains modified foam.

Foamed heat-resistance compares

Embodiment 1	Carbon yield (800 DEG C)/%
		Embodiment 2	77.88
Embodiment 3	77.12
		Embodiment 4	75.46
Embodiment 5	76.54
		Embodiment 6	74.68
Comparative example	55.23

Claims (10)

1. a kind of method for enhancing biomass phenolic foam heat resistance.This method is with the biomass material, boric acid, benzene of phenolic hydroxy group Phenol and paraformaldehyde are primary raw material, which is characterized in that this method includes three steps: the first step is the synthesis of boric acid phenolic ester. Acidic catalyst is added in the phenol of thawing, blending and stirring is uniform, add hydroxyl biomass and its derivative products and Boric acid is warming up to 110-140 DEG C, isothermal reaction 2-3h, separates the water that reaction generates using water segregator, prepares boric acid phenolic ester.The Two steps are the preparation of boron modification biomass foamed phenolic resin.The first step after the reaction was completed, is cooled to 55-65 DEG C, and alkalinity is added To 8.5-9.5, substep is added paraformaldehyde and is then warming up to 85-90 DEG C in 70-75 DEG C of reaction 1-1.5h catalyst tune pH value 2-3h is reacted, aldehyde agent, cooling discharge are tied up in addition.Third step is the preparation of phenol formaldehyde foam.Homemade boron modification biomass is foamed Phenolic resin is blended with blowing promotor, at a certain temperature foamed solidification, obtains the good biomass phenolic foam of heat resistance Plastics.

2. a kind of method for enhancing biomass phenolic foam heat resistance as described in claim 1, it is characterised in that: described contains The biomass material of phenolic hydroxyl group is mainly derived from two classes, and one kind is the effective component directly using biomass resource, such as wooden Element, anacardol, tannin, another kind of is to utilize biomass liquefying product and biomass pyrolysis product, such as Wood liquefied product, pyrolysis Oil and tar etc..

3. a kind of method for enhancing biomass phenolic foam heat resistance as described in claim 1, it is characterised in that:

The acidic catalyst is keggin heteropoly acid, such as phosphato-molybdic heteropolyacid, can also be with Dawson heteropoly acid, such as molybdenum vanadium phospha Polyacid；The base catalyst is sodium (potassium) base alkali or sodium (potassium) base alkalinity weak base salt, such as sodium hydroxide (potassium), sodium bicarbonate (potassium), sodium carbonate (potassium).

4. a kind of method for enhancing biomass phenolic foam heat resistance as described in claim 1, it is characterised in that: esterification 110-140 DEG C of temperature, isothermal reaction 2-3h, boric acid accounts for the 3-7% of the sum of biomass material and phenol quality.

5. a kind of method for enhancing biomass phenolic foam heat resistance as described in claim 1, it is characterised in that: phenolic aldehyde mole Than being 1: 1.5-1: 2.0.

6. a kind of method for enhancing biomass phenolic foam heat resistance as described in claim 1, it is characterised in that: described contains The biomass material of phenolic hydroxyl group accounts for the 10-15% of phenol quality.

7. a kind of method for enhancing biomass phenolic foam heat resistance as described in claim 1, it is characterised in that: the first step is anti- After the completion of answering, it is cooled to 55-65 DEG C, base catalyst tune pH value is added to 8.5-9.5, paraformaldehyde divides 3-4 step to be added, in 70- 75 DEG C of reaction 1-1.5h, are then warming up to 85-90 DEG C of reaction 2-3h.

8. a kind of method for enhancing biomass phenolic foam heat resistance as described in claim 1, it is characterised in that: described ties up Aldehyde agent is urea or melamine.

9. a kind of method for enhancing biomass phenolic foam heat resistance as described in claim 1, it is characterised in that: used consolidates Agent is phosphoric acid, p-methyl benzenesulfonic acid, dithyl sulfate and water, mass ratio 30-20: 50-70: 20-30: 40-50.

10. a kind of method for enhancing biomass phenolic foam heat resistance as described in claim 1, it is characterised in that: used Foaming formulation is as follows:

Nomenclature of drug Dosage/g Boron modification biomass phenolic resin 100 Foaming agent 6-10 Curing agent 15-30 Surfactant 2-5

Solidify 10-20min at 70-80 DEG C in a mold.