CN1257244C

CN1257244C - Composite phenolic resin glue producing method

Info

Publication number: CN1257244C
Application number: CN 200410097258
Authority: CN
Inventors: 曲韵丰
Original assignee: Individual
Current assignee: Individual
Priority date: 2004-08-03
Filing date: 2004-11-19
Publication date: 2006-05-24
Anticipated expiration: 2024-11-19
Also published as: CN1632030A

Abstract

The present invention discloses a production method for composite phenol aldehyde resin glue. NaOH is used as a catalyst, and phenol and formaldehyde carry out polycondensation reaction at the atmospheric pressure. The present invention is characterized in that sodium sulfonate lignin SSL is added in the reaction; a mol ratio of the phenol to the formaldehyde is 1/1.7 to 2.23; a weight ratio of the addition of each material in the sodium lignin sulfonate SSL, NaOH and dilution water to the phenol is 1/0.8 to 1.16; polydimethyl siloxane is used for controlling the reaction velocity; the reaction is carried out in a reaction vessel in four steps. The present invention has the advantages that the present invention has no formaldehyde and phenol sewage treatment problem in the production process; environment pollution can not be caused; only 160 to 180kg of phenol is used for producing one ton of the composite phenol aldehyde resin glue; the production cost is reduced by 20% to 30%; because of the addition of SSL, the defects of plates pressed by using ordinary phenol aldehyde resin glue as adhesive of high brittleness and high shrinkage ratio are overcome; experiments prove that the intensity of dried plates after being boiled in boiling water for 4 hours is not changed; the plates have no crack after being placed outdoors for four months.

Description

Composite phenolic resin glue producing method

Technical field

The present invention relates to a kind of Resin adhesive production method, more particularly, relate to the phenolic resin glue producing method that wood-based plate is used.

Background technology

Phenol aldehyde resin has good Joint strength and water tolerance, under hot and humid environment, has favorable durability, it is acidproof, the etch of chemically-resistant medicament, being a kind of excellent property adhesive of artificial board, is to find the earliest in the synthetic resins, realizes the kind of suitability for industrialized production at first, it is made through polycondensation by phenol and formaldehyde, heat-reactive phenolic resin glue is to make catalyzer with NaOH, carries out in reactor, its shortcoming is the production cost height, with raw materials used phenol is example, and home market price was about 8000 yuan per ton in 2003, then rose to 12000 yuan per ton in 2004, another then is that the wood-based plate fragility that makes of Phenol aldehyde resin is big, the shrinking percentage height.

Summary of the invention

The objective of the invention is to overcome the prior art deficiency, a kind of phenolic resin glue producing method that can reduce phenol usage and further improve the Phenol aldehyde resin performance is provided.

The production method of composite phenolic resin glue, with NaOH is catalyzer, carry out polycondensation by phenol and formaldehyde, production process is carried out in a reactor, and still has chuck outward, logical steam or water, being provided with agitator in the still is stirred, be reflected under the normal pressure and carry out, it is characterized in that, in reaction, add sodium lignosulfonate SSL; Reaction process is made up of reaction A section, reaction B section, reaction C section, reaction D section; The wherein raw materials used phenol purity 100% that requires, formaldehyde content 37%, caustic soda NaOH content 30%, sodium lignosulfonate SSL content is 98%, wherein sugared content 6%～8%; Described reaction A section drops into phenol, NaOH, sodium lignosulfonate SSL and dilution water, its amount, and NaOH and phenol weight ratio are 0.8～1.16, and SSL and phenol weight ratio are 0.8～1.16, and adding the dilution water yield and phenol weight ratio is 0.8～1.16; Stir, chuck feeds steam heating, and temperature is controlled at 43～50 ℃, keeps 25～35 minutes; 1. described reaction B section adds formaldehyde, and add-on is for adding 80% of total amount in the reaction, formaldehyde adds total amount and calculates phenol with phenol and formaldehyde mole ratio: feed process water in the formaldehyde 1: 1.7～2.23, chuck, make reactor temperature keep 43～50 ℃, kept 25～35 minutes; Described reaction C section, feed steam in the chuck, speed by 1 ℃ of per minute rising is promoted to 88～94 ℃ with reacting liquid temperature, be controls reaction speed, prevent bumping, prevent that promptly spray pot phenomenon from taking place, add polydimethylsiloxane in the still, its amount is 1 ‰ of reaction solution, is coated with 4 viscosity and reaches 18～19 seconds when (under 30 ℃ of conditions) when recording reaction solution, changes next conversion zone over to; Described reaction D section, too fast for preventing condensation polymerization speed, make the water-soluble reduction of product, reaction solution viscosity reaches and is coated with 4 viscosity after 18～19 seconds, reduces temperature of reaction rapidly, chuck leads to process water, or under the logical steam situation, do not discharge water or discharge water less, make reactor temperature reduce to 85 ℃, add formaldehyde more 2., its amount should add 20% of total amount for formaldehyde, under 85 ℃ of operational conditions, keeps 10 minutes, thereafter reacting liquid temperature can be increased to 88～90 ℃, reach 25～28.5 seconds (under 30 ℃ of conditions) when measuring reaction solution viscosity, reaction finishes, and is cooled to 40 ℃, blowing goes out finished product.

The invention has the advantages that:

1. owing to adopt sodium lignosulfonate to do additive and employing phenol and formaldehyde high molar ratio, 1: 2.23, the polycondensation method of not dewatering is produced Phenol aldehyde resin, formaldehydeless in the production process, phenol sewage handling problem can not constitute the pollution to environment, compliance with environmental protection requirements.

2. during general heat-reactive phenolic resin glue is produced, product per ton, will be with nearly 400kg phenol, and employing the present invention only just can produce one ton with 160kg phenol and meet the phenolic glue that standard GB/T14732-1993 requires, and production cost greatly reduces, calculate with chemical materials market cost of material in 2004, general Phenol aldehyde resin cost is 3000 yuan/ton, and by the invention process, as long as the composite phenolic resin glue cost is 2000 yuan/ton.

3. one of characteristics of the present invention just are that sodium lignosulfonate is arranged in the raw material, and it is the good absorption agent of formaldehyde, so, free aldehyde≤0.1% in the composite phenolic resin glue, the content of free phenol also is lower than national standard.

4. in the sodium lignosulfonate, it promptly has alcoholic extract hydroxyl group in constituting, and phenolic hydroxyl group and carbonyl functional group are arranged again, also contains 6%～8% carbohydrate simultaneously, participate in chemical reaction simultaneously, produce composite phenolic resin glue, overcome the big and high shortcoming of shrinking percentage of fragility after general employing phenolic glue is made sheet material, experiment shows, be pressed into plate with Resin adhesive of the present invention, boiled 4 hours with boiling water, after the drying, the intensity no change; Finished product is placed on outdoor, does not also have cracking phenomena and takes place in four months.

By the composite phenolic resin glue product that the present invention produces, through the quality supervised department check, the result is as shown in table 1.

Table 1

Interventions Requested	Unit	The national standard requirement	Assay	The individual event conclusion	Remarks
Interventions Requested	Unit	The national standard requirement	Assay	The individual event conclusion	Remarks	Outward appearance	-	Do not have mechanical impurity, sorrel is to the garnet transparent liquid		Qualified
PH value	-	10.0-12.0	10.5	Qualified		Outward appearance	-			Qualified
PH value	-	10.0-12.0	10.5	Qualified		Solids content	％	40.0-55.0	46	Qualified
Viscosity	mPa·S	300.0-1100.0	1010	Qualified		Solids content	％	40.0-55.0	46	Qualified
Viscosity	mPa·S	300.0-1100.0	1010	Qualified		The water Combination	Doubly	≥8	8	Qualified
Bonding strength	MPa	≥0.70	0.78	Qualified		The water Combination	Doubly	≥8	8	Qualified
Bonding strength	MPa	≥0.70	0.78	Qualified		Free phenol content	％	≤1.5	1.0	Qualified

Description of drawings

Fig. 1 is a process flow diagram of the present invention.

Fig. 2 is the present invention's reactor structural representation.

Embodiment

Below in conjunction with the drawings and specific embodiments the present invention is further described.

The said Phenol aldehyde resin of the present invention is meant with phenol and formaldehyde to be a kind of Phenol aldehyde resin of the thermosetting method production of basic raw material, main reaction:

Production process of the present invention is carried out in a reactor, and still has chuck outward, and logical steam is with heating, logical process water is with cooling, have agitator to stir in the still, the adding of phenol, formaldehyde is squeezed into reactor after vacuumizing by vacuum pump, and reaction process is carried out under normal pressure.Phenol requires content 100% in raw materials used; Formaldehyde requires content 37%; Additive sodium lignosulfonate SSL requires content 98%, wherein sugared content 6%～8%; Catalyzer caustic soda NaOH requires content 30%.

Embodiment 1, see Table 2, reacting the A section: NaOH, water, phenol are squeezed into reactor, NaOH weight, water weight is 1.16 times of phenol weight, start stirring, drop into sodium lignosulfonate, its weight is 1.16 times of phenol weight, fully stir, feed steam in the chuck, make temperature rise to 45 ℃, kept 30 minutes; Reaction B section: add formaldehyde, its amount is 80% of formaldehyde total amount, promptly this moment phenol with formaldehyde mole ratio 1: 1.78, adding the formaldehyde temperature can raise, chuck is gone into process water, makes temperature keep 45 ℃, lasting 30 minutes; Reaction C section: sodium lignosulfonate, phenol, formaldehyde reacts under catalyst n aOH effect, chuck feeds steam, is warming up to 94 ℃ by slow the overflowing of the speed of 1 ℃ of per minute intensification, when finding bumping or bumping phenomenon sign is arranged, add a little polydimethylsiloxane controls reaction speed, be coated with 4 viscosity (under 30 ℃ of conditions) when being 18 seconds when what measure reactant, this section reaction finishes, reaction D section: too fast for preventing speed of response, avoid the water-soluble reduction of resultant, after being coated with 4 viscosity and reaching 18 seconds, reduce temperature rapidly, to 85 ℃, add formaldehyde again, making phenol and formaldehyde (cumulative amount) mol ratio is 1: 2.23, under 85 ℃ of temperature, keeps reaction 10 minutes, after this, slowly be warming up to 88 ℃ again, be coated with 4 viscosity and reach 25 seconds (under 30 ℃ of conditions) recording, the logical process water of chuck is cooled to 40 ℃ rapidly again, blowing, go out finished product, related data is recorded in table 2.

The situation of embodiment 2,3,4,5, except that every record data in the table 2, process condition is all with embodiment 1.

Table 2

Phenol and formaldehyde are mol ratio in the ※ proportioning, and all the other are weight ratio.

Claims

1, a kind of composite phenolic resin glue producing method, with NaOH is catalyzer, carry out polycondensation by phenol and formaldehyde, production process is carried out in a reactor, still has chuck outward, is provided with stirring in the still, is reflected under the normal pressure and carries out, it is characterized in that, in reaction, add sodium lignosulfonate SSL; Reaction process is made up of reaction A section, reaction B section, reaction C section, reaction D section; Described reaction A section drops into phenol, NaOH, sodium lignosulfonate SSL, dilution water, add-on, and the weight ratio of NaOH, sodium lignosulfonate SSL, dilution water and phenol add-on is 0.8～1.16, and temperature is controlled at 43～50 ℃, keeps 25～35 minutes; 1. described reaction B section adds formaldehyde, and add-on is for adding 80% of total amount in the reaction, and formaldehyde adds total amount and calculates with phenol and formaldehyde mole ratio, and phenol: formaldehyde=1: 1.7～2.23, temperature are controlled at 43～50 ℃, keep 25～35 minutes; Described reaction C section feeds steam in the chuck, with rise 1 ℃ speed of per minute, makes reaction solution be promoted to 83～94 ℃, adds polydimethylsiloxane, and its amount is reaction solution 1 ‰, when reaction solution when being coated with 4 viscosity and reaching 18～19 seconds, change next conversion zone over to; Described reaction D section, after reactor temperature is reduced to 85 ℃, add formaldehyde 2., its amount should add 20% of total amount for formaldehyde, and under 85 ℃ of conditions, reaction was kept 10 minutes, thereafter reaction solution is warming up to 88～90 ℃, reach 25～28.5 seconds when reaction solution is coated with 4 viscosity, finish reaction, wherein be coated with 4 viscosimetric analysis and under 30 ℃ of conditions, carry out.