CN1257245C

CN1257245C - Method for producing composite SSL-UF urea-formaldehyde resin glue

Info

Publication number: CN1257245C
Application number: CN 200410010993
Authority: CN
Inventors: 曲韵丰
Original assignee: Individual
Current assignee: Individual
Priority date: 2004-07-12
Filing date: 2004-07-12
Publication date: 2006-05-24
Anticipated expiration: 2024-07-12
Also published as: CN1594479A

Abstract

The present invention discloses a method for producing composite SSL-UF urea-formaldehyde resin adhesive, which is characterized in that the technological process is composed of modification and addition reaction section A, condensation reaction section A, condensation reaction section B and addition reaction section B; the present invention comprises the components and the formula thereof: the molar ratio of urea to formaldehyde is 1: 1.5 to 1.65; ammonium lignosulfonate SSL measured by weight accounts for 15 to 20% of formaldehyde; polyvinyl alcohol measured by weight accounts for 1 to 1.4% of urea; reaction is carried out in a reaction vessel with a jacket under ordinary pressure, steam is filled in the jacket in order to heat, and water is filled in the jacket in order to cool; methanoic acid and sodium hydroxide are used as catalysts to control PH values. The present invention has the advantages of no dehydration in production, no harm and handling problem of formaldehyde polluted water, high strength, aging resistance, low cost and cheap sale price. The content of the formaldehyde in products achieves the environmental protection requirements and is less than 0.15%, and the adhesive can be used for producing veneer boards, multilayer boards, blockboards and E1 level artificial boards.

Description

Compound SSL-UF urea resin gel

Technical field

The present invention relates to a kind of Resin adhesive production method, more particularly, relate to compound urea resin gel.

Background technology

At present, domestic Wood-based Panel Production, the urea-formaldehyde glue as shaving board, glued board, multi-ply wood, core-board production are all adopted.Limited by production cost, the properties-correcting agent addition is few in the glue, and the performance of producing tackiness agent is undesirable, the artificial board of compacting of poor quality, if improve the properties-correcting agent addition, then production cost can greatly improve, and the user is difficult to accept; Adopt existing method, with urea, formaldehyde, polyvinyl alcohol, through addition, polycondensation, N-process, the urea-formaldehyde glue of producing, the content of free aldehyde height, ageing-resistant poor performance, production cost expense height has pollution to environment.

Summary of the invention

The objective of the invention is to overcome the prior art deficiency, a kind of compound urea resin gel is provided, it is low to produce a kind of content of free aldehyde, ageing-resistant, the Resin adhesive that processing performance is good.

Production process of the present invention is carried out in reactor, there is agitator to stir in the reactor, chuck is arranged, with steam with the heating, water is with cooling, institute responds and all carries out under normal pressure, and it is characterized in that: its prescription is that urea and formaldehyde mole ratio are 1: 1.5～1.65, and the SSL of ammonium lignosulphonate consumption is 15%～20% (a weight meter) of formaldehyde amount; Polyvinyl alcohol (PVA) amount is 1.0%～1.4% (weight meter) of urea amount; Catalyzer formic acid is in order to regulate pH value, and catalyzer caustic soda (NaOH) is in order to regulate pH value, and polydimethylsiloxane is used for controls reaction speed, takes place to avoid the bumping phenomenon.

Technological process of the present invention is divided into modification, addition reaction A section, condensation reaction A section, condensation reaction B section, five steps of addition reaction B section, described modification, be to do under the catalyzer condition at caustic soda, the modification of ammonium lignosulphonate (SSL) is under vacuum condition, formaldehyde sucting reaction still, normal pressure drops into ammonium lignosulphonate down, and regulating pH value with caustic soda is 7.6～8.0, logical steam in the chuck, temperature is controlled at 92～95 ℃, and reaction was kept 30～40 minutes; Described addition reaction A section drops into urea, and it is measured in molar ratio, urea: formaldehyde=1: 2, add polyvinyl alcohol, it is measured to 1.0%～1.4% (weight) of urea total amount, is generally 1.2%, temperature is controlled at 88～92 ℃, and pH value 7.6～8.0 kept 30～40 minutes; Described condensation reaction A section, temperature is controlled at 88～92 ℃, adds formic acid, regulates pH value 5.4～5.6, for preventing the bumping phenomenon, adds polydimethylsiloxane in right amount, is reacted to measure to be coated with 4 viscosity and to reach 19-20 second (under 30 ℃ of conditions), reacts 60～80 minutes; Described condensation reaction B section drops into urea, the urea that add up this moment: formaldehyde=1: 1.7 (mol ratio), and the chuck water flowing, reactant is cooled to 85～87 ℃, adds caustic soda, regulates pH value 5.7～5.95, and reaction is 25～28.5 seconds (under 30 ℃ of conditions) to being coated with 4 viscosity; Described addition reaction B section adds caustic soda again, makes the reaction solution pH value reach 7.6～8.0, the chuck water flowing is cooled to 70～80 ℃, adds urea, mol ratio between this moment urea total amount and formaldehyde amount, urea: formaldehyde=1: 1.5～1.65, cooling keeps after 30～40 minutes at 65 ℃, be cooled to 40 ℃ again, blowing, packing goes out finished product.

Compound SSL-UF urea-formaldehyde resin adhesive product the key technical indexes such as table 1.

Table 1

Outward appearance	Brown liquid
Outward appearance	Brown liquid	Viscosity	25～28.5s (being coated with 430 ℃)
Free aldehyde	0.04％～0.15％	Viscosity	25～28.5s (being coated with 430 ℃)
Free aldehyde	0.04％～0.15％	Solid content	52％～60％
Curing speed	110s～260s	Solid content	52％～60％
Curing speed	110s～260s	Storage period	〉=30 days (under 5～20 ℃ of conditions)
Hot pressing temperature	105℃～120℃	Storage period	〉=30 days (under 5～20 ℃ of conditions)
Hot pressing temperature	105℃～120℃	Hot pressing pressure	1.5MPa～2.0MPa
Amount of spread (two-sided)	200g/m ²～240g/m ²(the thin plate water ratio is 8%～12%)	Hot pressing pressure	1.5MPa～2.0MPa
Amount of spread (two-sided)	200g/m ²～240g/m ²(the thin plate water ratio is 8%～12%)	Amount of spread (two-sided)	200g/m ²～220g/m ²(the thin plate water ratio is 8%～10%)

The invention has the advantages that:

1, do not dewater in the production process, do not need formaldehyde sewage disposal operation, environmentally safe.

2, free aldehyde is lower than 0.15% in the glue, its performance is higher than " material industry tackiness agent urea aldehyde, phenolic aldehyde, terpolycyantoamino-formaldehyde resin " GB/T14732-93 requirement, standard-required solids content 46%～52%, the free formaldehyde content standard-required is≤1.0%, and this product solids content 52%～62%, free formaldehyde content is 0.04%～0.15%, and this glue can be used for E1 level environmental requirement Wood-based Panel Production.

3, the bonding strength of compound SSL-UF urea-formaldehyde resin adhesive, weather resistance, water tolerance and Amount of spread obviously are better than common urea-formaldehyde resin.In the plate test that carried out in 2003, single spreading amount 85g/m ², so low Amount of spread has reduced the unit cost of wood-based plate significantly, and at four months no cracking phenomenas of outdoor placement, model soaked one month under room temperature, and the intensity of dry back model does not have considerable change.The highest 24% of the amount of resin that adds to of weighting agent during impregnation, pressing plate glue consumption obviously reduce and intensity is constant.

4, high solids content.Its solid content of dehydrated glue on the market is 60% at present, and its solid content of non-dehydrated glue is only about 48%; And the urea-formaldehyde resin non-dehydrated solid content of compound SSL-UF promptly reaches 52%～60%.So this glue as mentioned above, uses 85g/m ²Amount of spread, just can reach goodish intensity.This advantage is that any non-dehydrated glue is beyond one's reach.

5, initial viscosity height.Be particularly suitable for precompressed and produce wood-based plate.In plate test in 2003, enter preformer behind the gluing, pressure 1.4Mpa, 20 minutes time was moulding after the release, and with the urea-formaldehyde glue of the other types on the market, the shortest squeeze time was also wanted about 40 minutes, have in addition the longer time.

6, storage period is long.The storage period of compound SSL-UF urea-formaldehyde resin adhesive between 5～20 ℃ was above one month.

Description of drawings

Fig. 1 is a technological process block diagram of the present invention

Embodiment

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

Production process of the present invention is carried out in a reactor, has agitator to stir in the still, and still has chuck outward, and logical steam is with heating, and water flowing is with cooling.The formation reaction of described urea aldehyde is

One of feature of the present invention is to have added the SSL of ammonium lignosulphonate sizing in the reaction, it is good formaldehyde absorption agent, so needn't dewater in the production process, it is the reason of formaldehydeless aqueous waste solution pollution problem, it also is the free low reason of aldehyde in the product, the SSL of ammonium lignosulphonate adds, containing sugared quantity in its ammonium lignosulphonate must guarantee in 6%～8% conditional request, meaning also is to have more hydroxyl in the SSL sizing structure, exist with alcoholic extract hydroxyl group and two kinds of forms of phenolic hydroxyl group, so can with formaldehyde generation condensation reaction, generate macromolecular compound, be similar to phenol thing and formaldehyde condensation polymer and generate the resol process, the carbohydrate in the SSL sizing and self contain the alcoholic extract hydroxyl group thing and formaldehyde condensation generates furfuryl resin, this is the reason place of being called composite resin glue.

Technological process of the present invention comprises modification, addition reaction A section, condensation reaction A section, condensation reaction B section, addition reaction B section.Embodiment 1 used urea content 98%; Formaldehyde content 36.5%, ammonium lignosulphonate's content 98% contains sugar 8%; Described modification, under vacuum, formaldehyde sucting reaction still, normal pressure drop into ammonium lignosulphonate down, and its amount is 15% with the formaldehyde weight ratio, drives agitator and stirs, and adds formic acid, adjusts PH7.6, and chuck leads to steam, and temperature is controlled at 92 ℃, and reaction was held time T40 minute; Described addition A section, the chuck water flowing, temperature is reduced to 40 ℃, drops into urea, it is measured in molar ratio, urea: formaldehyde=1: 2, add polyvinyl alcohol, and its amount is urea amount 1.2% (weight meter), stir, lead to steam, heat up 88 ℃, the pH value value keeps 7.6, hold-time T40 minute; Described condensation reaction A section stirs, heats 88 ℃, adds formic acid and transfers pH value 5.4, and the existing bumping phenomenon of desire adds a little polydimethylsiloxane, and to be coated with 4 viscosity be 19 seconds (under 30 ℃ of conditions) to measuring in reaction, reacted 80 minutes; Described condensation reaction B section drops into urea, at this moment urea: formaldehyde=1: 1.7 (mol ratio), to stir, and the chuck water flowing is cooled to 80 ℃, adds caustic soda, transfers PH5.7, and reaction is 28 seconds (under 30 ℃ of conditions) to being coated with 4 viscosity; Described addition reaction B section adds caustic soda again and makes PH=7.6, stirs, and the chuck water flowing is cooled to 75 ℃, adds urea, at this moment urea: formaldehyde=1: 1.5, after keeping 40 minutes, be cooled to 0 ℃ again, and blowing goes out finished product.

All the other 2,3,4 embodiment, except that in the table 2 listed every, other condition is identical.

Table 2

※ T time unit is for dividing

Compound SSL-UF urea-formaldehyde resin adhesive, not only performance is good, and content of free aldehyde reaches the requirement of environmental protection glue, production cost is also low, at present, environmental protection urea-formaldehyde resin adhesive price is 2100～2400 yuan/tons on the market, and 1500～1700 yuan/tons of compound SSL-UF urea-formaldehyde resin adhesive prices.

Claims

1, a kind of compound SSL-UF urea resin gel is characterized in that:

Produce materials and fill a prescription as follows:

Urea and formaldehyde mole ratio are 1: 1.5～1.65;

Ammonium lignosulphonate's consumption is 15%～20% of a formaldehyde amount, by weight;

The polyvinyl alcohol consumption is 1%～1.4% of a urea amount, by weight;

Technological process is made of modification, addition reaction A section, condensation reaction A section, condensation reaction B section, addition reaction B section; Described modification is meant at caustic soda and does under the catalyzer condition ammonium lignosulphonate's modification, under vacuum condition, formaldehyde sucting reaction still, normal pressure drop into ammonium lignosulphonate down, transferring pH value with caustic soda is 7.6～8.0, and temperature is controlled at 92～95 ℃, and reaction was kept 30～40 minutes; Described addition reaction A section, drop into urea, urea: formaldehyde=1: 2, mol ratio adds polyvinyl alcohol, and for urea amount is 1.0%～1.4%, temperature is controlled at 88～92 ℃, and pH value 7.6～8.0 kept 30～40 minutes; Described condensation reaction A section, temperature is controlled at 88～92 ℃, adds formic acid, transfers pH value 5.4～5.6, is coated with 4 viscosity, is 19～20 seconds under 30 ℃ of conditions, reacts 60～80 minutes; Described condensation reaction B section drops into urea, its cumulative investment urea total amount and formaldehyde amount ratio, and urea: formaldehyde=1: 1.7, mol ratio, temperature are controlled at 85～87 ℃, add caustic soda, transfer pH value 5.7～5.95, are coated with 4 viscosity, are 25～28.5 seconds under 30 ℃ of conditions; Described addition reaction B section, add caustic soda again, make reaction solution pH value 7.6～8.0, the chuck water flowing, be cooled to 70～80 ℃, add urea, this moment urea total amount and formaldehyde total amount mol ratio, urea: formaldehyde=1: 1.5～1.65, cooling is at 65 ℃, after keeping 30～40 fens kinds, be cooled to 40 ℃ again, blowing, pack, go out finished product.

According to the described compound SSL-UF urea resin gel of claim 1, it is characterized in that 2, described condensation reaction A section adds the polydimethylsiloxane controls reaction speed in right amount, prevent that the bumping phenomenon from taking place.