CN104212122B - The additive of a kind of resol, preparation method and application - Google Patents

Abstract

The present invention discloses the additive of a kind of resol, preparation method and application, belongs to timber sizing agent field. Described additive mainly comprises cake of camellia oleifera seeds, linking agent, curing catalyst, stablizer and water. Cake of camellia oleifera seeds powder is dispersed in water, adds linking agent and also stir evenly, insulation reaction 2��3h at 50��70 DEG C, it is cooled to 30 DEG C, add curing catalyst and stablizer, stir evenly and insulation reaction 0.5��1h, obtain the additive of described resol; Described additive application is in phenolic resin adhesive, can effectively improve curing speed and the bonding strength of phenolic resin adhesive, shorten the hot pressing time of glued board and significantly improve its water resistance, and then raising production efficiency, reduce energy consumption and manufacturing cost, there is the social effect of energy-saving and emission-reduction; Described preparation method is simple, easy and simple to handle.

Description

The additive of a kind of resol, preparation method and application

Technical field

The present invention relates to the additive of a kind of resol, preparation method and application, it is specifically related to additive, the preparation method of a kind of wood-based plate resol and contains described additive application in phenolic resin adhesive, belong to timber sizing agent field.

Background technology

Resol (PF resin) is the synthetic resins realizing industrialization in the world the earliest, mainly for the manufacture of various plastics, coating, tackiness agent, synthon, fire-retardant material etc., is very important macromolecular material. Resol has Joint strength height, resistance to boiling water, heat-resisting, weather-proof as tackiness agent, and the advantages such as resistance to chemical attack, are widely used in wood processing field, are the conventional tackiness agent of outdoor structure wood-based plate. In recent years, along with building, transport field are to the increase of the engineering materials demands such as oriented wood chipboard, cord-wood, container bottom board, the market outlook of outdoor wood-based plate are very wide, the annual production of PF resin is increased year by year, 650,000 t of 2013 it are increased to from 260,000 t of 2007, amplification shows wide development space up to 150%, PF resin. But, expensive due to phenol, the price making resol all the time according to height not under, and resol self also also exists some shortcomings, as solidification after glue-line firmly crisp, easily chap, particularly curing speed is relatively slow compared with other aminoresin, and these cause resol and glued joint that the price of goods is relatively high, production efficiency is not high, limit synvaren and apply widely.

By adding low cost material in resol, reduce the cost of resol, for the Application Areas expanding resol, there is important meaning. Usually adopt bean powder, degreasing soybean protein powder and flour etc. to reduce the cost of resol, but due to these materials be the raw material of some agricultural and sideline food, price is higher, and the amplitude therefore reducing resol cost is very limited. And the interpolation of these materials usually can cause length set time of resol, the shortcoming such as Joint strength is low, working life is short, usability is poor. Resol adds the curing speed that the carbonate such as such as sodium carbonate can improve resin, but reduces the working life that resin can be caused, the shortcoming such as bonding strength attenuating.

Summary of the invention

For above-mentioned defect, an object of the present invention is to provide the additive of a kind of resol, and described additive is cheap, reactive behavior height, can significantly reduce the cost of resol, increases substantially curing speed and the bonding strength of resol. The two of object are to provide the preparation method of the additive of a kind of resol, and described method is simple, easy and simple to handle;

It is an object of the invention to be achieved through the following technical solutions.

An additive for resol, taking described additive total mass as 100%, each component and mass percentage are as follows:

Wherein, cake of camellia oleifera seeds is the solid matter remained after the Extraction oil of seed tea-seed oil of oil tea (Camelliaoleifera), and taking cake of camellia oleifera seeds total mass as 100%, camellia seed oil content is less than 10%, and the granularity of cake of camellia oleifera seeds is less than 200 orders;

The preferred cyanurotriamide modified urea resin performed polymer of linking agent, its preparation method is as follows:

Urea, formaldehyde and trimeric cyanamide are mixed, adds formic acid, stir evenly; Being heated to 85 DEG C, insulation is 12��15 seconds to being coated with 4 viscosity, is cooled to 70 DEG C, adds sodium hydroxide solution, adjust pH to 7.5, and reaction 15min, is cooled to 30 DEG C, discharging, obtains described cyanurotriamide modified urea resin performed polymer;

Wherein, the preferred 1:1.3:0.05:0.01 of the mass ratio of described urea, formaldehyde, trimeric cyanamide and formic acid;

In sodium hydroxide solution, the massfraction of sodium hydroxide is 30%;

More than one in the preferred sodium carbonate of curing catalyst, glycerol acetate and propylene carbonate;

More than one in stablizer preferably phosphoric acid sodium dihydrogen, Sodium phosphate dibasic, borax and Sodium Benzoate;

A preparation method for the additive of resol, described method concrete steps are as follows:

(1) cake of camellia oleifera seeds powder is dispersed in water, adds linking agent and also stir evenly, obtain mixture a; By mixture a insulation reaction 2��3h at 50��70 DEG C, obtain mixture b;

(2) mixture b is cooled to 30 DEG C, adds curing catalyst and stablizer, stir evenly and insulation reaction 0.5��1h, obtain the additive of resol of the present invention;

The additive application of a kind of resol is in phenolic resin adhesive, and phenolic resin adhesive is made up of additive and resol;

Wherein, resol is solid content is 40��50%, and apparent viscosity is the heat-reactive phenolic resin of 150��1500 centipoises;

The mass ratio of additive and resol preferably 20��30:100.

Useful effect

(1) cake of camellia oleifera seeds contained in additive of the present invention belongs to agricultural machining waste, and price is very cheap, it is possible to reduce the cost of phenolic resin adhesive; And cake of camellia oleifera seeds contains abundant protein, tannin, tea saponin and robust fibre, these materials solidify time can with resol generation crosslinking reaction, it it is the additive that resol is good, the consumption of the tradition resol filler such as flour, soybean protein can be reduced, effectively reduce the consumption of grain;

(2) curing catalyst contained in additive of the present invention and linking agent, can effectively improve the curing speed of phenolic resin adhesive, shorten the hot pressing time of the wood-based plate of preparation, the methylol of linking agent and amino group can with the active group polymerization reaction take place of resol, and then improve the bonding strength of resin;

(3) containing stablizer in additive of the present invention, it is possible to effectively after guarantee interpolation additive of the present invention, phase working life of resol is not influenced, makes phenolic resin adhesive have good usability;

(4) preparation method of solidifying agent of the present invention is simple, easy and simple to handle.

Embodiment

With specific embodiment in detail the present invention is described in detail below, but it is not limited to this.

Mentioning resol in following examples is heat-reactive phenolic resin, produces by Tai Er chemical industry (Beijing) company limited, and other main agents information is in table 1; Main instrument and equipment information is in table 2;

Table 1

Table 2

Cake of camellia oleifera seeds is the solid matter remained after the Extraction oil of seed tea-seed oil of oil tea (Camelliaoleifera), and taking cake of camellia oleifera seeds total mass as 100%, camellia seed oil content is 8%, and the granularity of cake of camellia oleifera seeds is 200 orders;

In sodium hydroxide solution, the massfraction of sodium hydroxide is 30%.

Embodiment 1

An additive for resol, taking described additive total mass as 100%, each component and mass percentage are as follows:

A preparation method for the additive of resol, described method concrete steps are as follows:

(1) 10kg urea, 13kg formaldehyde and 0.5kg trimeric cyanamide are mixed, add 0.1kg formic acid, stir evenly; Being heated to 85 DEG C, insulation is 12 seconds to being coated with 4 viscosity, is cooled to 70 DEG C, adds 30% sodium hydroxide solution, adjust pH to 7.5, and reaction 15min, is cooled to 30 DEG C, discharging, obtains cyanurotriamide modified urea resin performed polymer;

(2) 50kg cake of camellia oleifera seeds powder is dispersed in 40kg water, adds 5kg cyanurotriamide modified urea resin performed polymer and also stir evenly, obtain mixture a; By mixture a insulation reaction 2h at 50 DEG C, obtain mixture b;

(3) mixture b is cooled to 30 DEG C, adds 4.5kg sodium carbonate and 0.5kg SODIUM PHOSPHATE, MONOBASIC, stir evenly and insulation reaction 1h, obtain the additive of resol.

The main technical indicator of gained resol additive is: solids content is 56%, pH is 8.2, storage period >=10 days.

(4) step (3) described additive and resol are stirred evenly (mass ratio of additive and resol is 30:100), obtain phenolic resin adhesive (being numbered sizing agent 1), wherein resol parameter is: solid content is 40%, and apparent viscosity is 150 centipoises.

Embodiment 2

An additive for resol, taking described additive total mass as 100%, each component and mass percentage are as follows:

A preparation method for the additive of resol, described method concrete steps are as follows:

(1) 10kg urea, 13kg formaldehyde and 0.5kg trimeric cyanamide are mixed, add 0.1kg formic acid, stir evenly; Being heated to 85 DEG C, insulation is 15 seconds to being coated with 4 viscosity, is cooled to 70 DEG C, adds 30% sodium hydroxide solution, adjust pH to 7.5, and reaction 15min, is cooled to 30 DEG C, discharging, obtains cyanurotriamide modified urea resin performed polymer;

(2) 20kg cake of camellia oleifera seeds powder is dispersed in 58kg water, adds 15kg cyanurotriamide modified urea resin performed polymer and also stir evenly, obtain mixture a; By mixture a insulation reaction 3h at 70 DEG C, obtain mixture b;

(3) mixture b is cooled to 30 DEG C, adds 5kg glycerol acetate and 2kg borax, stir evenly and insulation reaction 0.5h, obtain the additive of resol.

The main technical indicator of gained resol additive is: solids content is 35%, pH is 7.8, storage period >=10 days.

(4) step (3) described additive and resol are stirred evenly (mass ratio of additive and resol is 20:100), obtain phenolic resin adhesive (being numbered sizing agent 2), wherein resol parameter is: solid content is 50%, and apparent viscosity is 1500 centipoises.

Embodiment 3

An additive for resol, taking described additive total mass as 100%, each component and mass percentage are as follows:

A preparation method for the additive of resol, described method concrete steps are as follows:

(1) 10kg urea, 13kg formaldehyde and 0.5kg trimeric cyanamide are mixed, add 0.1kg formic acid, stir evenly; Being heated to 85 DEG C, insulation is 13 seconds to being coated with 4 viscosity, is cooled to 70 DEG C, adds 30% sodium hydroxide solution, adjust pH to 7.5, and reaction 15min, is cooled to 30 DEG C, discharging, obtains cyanurotriamide modified urea resin performed polymer;

(2) 20kg cake of camellia oleifera seeds powder is dispersed in 70kg water, adds 6kg cyanurotriamide modified urea resin performed polymer and also stir evenly, obtain mixture a; By mixture a insulation reaction 2.5h at 60 DEG C, obtain mixture b;

(3) mixture b is cooled to 30 DEG C, adds 3kg propylene carbonate and 1kg Sodium Benzoate, stir evenly and insulation reaction 0.8h, obtain the additive of resol.

The main technical indicator of gained resol additive is: solids content is 26%, pH is 7.6, storage period >=10 days.

(4) step (3) described additive and resol are stirred evenly (mass ratio of additive and resol is 25:100), obtain phenolic resin adhesive (being numbered sizing agent 3), wherein resol parameter is: solid content is 45%, and apparent viscosity is 800 centipoises.

Embodiment 4

An additive for resol, taking described additive total mass as 100%, each component and mass percentage are as follows:

A preparation method for the additive of resol, described method concrete steps are as follows:

(1) 10kg urea, 13kg formaldehyde and 0.5kg trimeric cyanamide are mixed, add 0.1kg formic acid, stir evenly; Being heated to 85 DEG C, insulation is 14 seconds to being coated with 4 viscosity, is cooled to 70 DEG C, adds 30% sodium hydroxide solution, adjust pH to 7.5, and reaction 15min, is cooled to 30 DEG C, discharging, obtains cyanurotriamide modified urea resin performed polymer;

(2) 30kg cake of camellia oleifera seeds powder is dispersed in 55kg water, adds 10kg cyanurotriamide modified urea resin performed polymer and also stir evenly, obtain mixture a; By mixture a insulation reaction 3h at 65 DEG C, obtain mixture b;

(3) mixture b is cooled to 30 DEG C, adds 1.5kg propylene carbonate, 2kg sodium carbonate and 1.5kg Sodium phosphate dibasic, stir evenly and insulation reaction 0.6h, obtain the additive of resol.

The main technical indicator of gained resol additive is: solids content is 43%, pH is 8.0, storage period >=10 days.

(4) step (3) described additive and resol are stirred evenly (mass ratio of additive and resol is 25:100), obtain phenolic resin adhesive (being numbered sizing agent 4), wherein resol parameter is: solid content is 48%, and apparent viscosity is 1000 centipoises.

Embodiment 5

An additive for resol, taking described additive total mass as 100%, each component and mass percentage are as follows:

A preparation method for the additive of resol, described method concrete steps are as follows:

(1) 10kg urea, 13kg formaldehyde and 0.5kg trimeric cyanamide are mixed, add 0.1kg formic acid, stir evenly; Being heated to 85 DEG C, insulation is 12 seconds to being coated with 4 viscosity, is cooled to 70 DEG C, adds 30% sodium hydroxide solution, adjust pH to 7.5, and reaction 15min, is cooled to 30 DEG C, discharging, obtains cyanurotriamide modified urea resin performed polymer;

(2) 40kg cake of camellia oleifera seeds powder is dispersed in 45kg water, adds 10kg cyanurotriamide modified urea resin performed polymer and also stir evenly, obtain mixture a; By mixture a insulation reaction 2.5h at 70 DEG C, obtain mixture b;

(3) mixture b is cooled to 30 DEG C, adds 3kg sodium carbonate, 1kg borax and 1kg SODIUM PHOSPHATE, MONOBASIC, stir evenly and insulation reaction 1h, obtain the additive of resol.

The main technical indicator of gained resol additive is: solids content is 48%, pH is 8.4, storage period >=10 days.

(4) step (3) described additive and resol are stirred evenly (mass ratio of additive and resol is 23:100), obtain phenolic resin adhesive (being numbered sizing agent 5), wherein resol parameter is: solid content is 45%, and apparent viscosity is 500 centipoises.

Embodiment 6

An additive for resol, taking described additive total mass as 100%, each component and mass percentage are as follows:

A preparation method for the additive of resol, described method concrete steps are as follows:

(1) 10kg urea, 13kg formaldehyde and 0.5kg trimeric cyanamide are mixed, add 0.1kg formic acid, stir evenly; Being heated to 85 DEG C, insulation is 12 seconds to being coated with 4 viscosity, is cooled to 70 DEG C, adds 30% sodium hydroxide solution, adjust pH to 7.5, and reaction 15min, is cooled to 30 DEG C, discharging, obtains cyanurotriamide modified urea resin performed polymer;

(2) 35kg cake of camellia oleifera seeds powder is dispersed in 50kg water, adds 8kg cyanurotriamide modified urea resin performed polymer and also stir evenly, obtain mixture a; By mixture a insulation reaction 2h at 60 DEG C, obtain mixture b;

(3) mixture b is cooled to 30 DEG C, adds 3kg sodium carbonate, 2kg glycerol acetate and 1.5kg Sodium Benzoate, 0.5kg borax, stir evenly and insulation reaction 0.5h, obtain the additive of resol.

The main technical indicator of gained resol additive is: solids content is 42%, pH is 7.8, storage period >=10 days.

(4) step (3) described additive and resol are stirred evenly (mass ratio of additive and resol is 20:100), obtain phenolic resin adhesive (being numbered sizing agent 6), wherein resol parameter is: solid content is 45%, and apparent viscosity is 150 centipoises.

Embodiment 7

Utilizing following test to prove the effect of phenolic resin adhesive prepared by embodiment 1��6, particular content is as follows:

With the direct additive as a comparison of flour, stirring evenly (mass ratio of flour and resol is 30:100) by flour and resol, obtain comparison sizing agent, wherein resol parameter is: solid content is 40%, and apparent viscosity is 150 centipoises.

Phenolic resin adhesive embodiment 1��6 prepared respectively and comparison tackiness agent are cured velocity test, detection working life and 5 layers of poplar plywood preparation.

Wherein, the test of curing speed and working life carries out according to the corresponding method of detection of regulation in GB/T14074-2006 " wood adhesive and the resin method of inspection thereof ", and the probe temperature of curing speed is 130 DEG C, and test result is as shown in table 1.

During preparation 5 layers of glued board, veneer is 5 years quick growth poplar wood veneers (length 400 millimeters, width 400 millimeters, thickness 1.7 millimeters), water ratio 12%; The heat pressing process of 5 layers of glued board is: 1.0Mpa, and temperature is 130 DEG C, and the time is 5 minutes.

The tackiness agent obtained according to the type �� plywood bonding strength testing method testing example of regulation in GB/T17657-1999 " test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels " and the bonding strength compareing 5 layers of glued board prepared by tackiness agent, result is as shown in table 1.

Table 1

As seen from Table 1, the phenolic resin adhesive prepared by embodiment of the present invention 1-6 method relatively compares the curing speed of tackiness agent respectively fast 20.3%, 20.0%, 23.9%, 22.1%, 19.2% and 21.6%; Meanwhile, the working life of phenolic resin adhesive prepared by embodiment 1-6 method is also long than the working life of comparison tackiness agent. Therefore, the additive prepared by the inventive method can effectively improve the curing speed of resol, extends the working life of resol.

In addition, it can also be seen that by table 1, after the additive adopting the inventive method to prepare mixes with resol, the bonding strength of its phenolic resin adhesive obtained is higher than the bonding strength of the phenolic resin adhesive obtained using flour as additive, it thus is seen that additive prepared by the inventive method can effectively improve the bonding strength of phenolic resin adhesive.

Cost analysis:

At present, phenol price is greatly about 13000 yuan/ton, the cost of the resol of 40% solids content is about 4000 yuan/ton, and cake of camellia oleifera seeds is agricultural machining by product, cheap, only 1500 yuan/ton (dry-matter), the cost of the resol additive prepared with it (solids content 56%) is about 1300 yuan/ton to price; And flour is about 3200 yuan/ton as the market value of additive. Therefore, it is possible to calculate the cost of the various phenolic resin adhesives containing resol additive as shown in table 2.

Table 2

As shown in Table 2, after the additive of the present invention joins resol, can significantly lower the cost value of phenolic resin adhesive, and compared with the additive flour conventional with resol, its price advantage is obvious.

The present invention includes but not limited to above embodiment, and every any equivalent replacement of carrying out under the principle of spirit of the present invention or local improvement, all will be considered as within protection scope of the present invention.

Claims (6)

1. the additive of a resol, it is characterised in that: taking described additive total mass as 100%, each component and mass percentage are as follows:

Wherein, described linking agent is cyanurotriamide modified urea resin performed polymer.

2. the additive of a kind of resol according to claim 1, it is characterized in that: described cake of camellia oleifera seeds is the solid matter remained after the Extraction oil of seed tea-seed oil of oil tea, taking cake of camellia oleifera seeds total mass as 100%, wherein, camellia seed oil content is less than 10%, and the granularity of cake of camellia oleifera seeds is less than or equal to 200 orders.

3. the additive of a kind of resol according to claim 1, it is characterised in that: the preparation method of described cyanurotriamide modified urea resin performed polymer is as follows:

Urea, formaldehyde and trimeric cyanamide are mixed, adds formic acid, stir evenly; Being heated to 85 DEG C, insulation is 12��15 seconds to being coated with 4 viscosity, is cooled to 70 DEG C, adds sodium hydroxide solution, adjust pH to 7.5, and reaction 15min, is cooled to 30 DEG C, discharging, obtains described cyanurotriamide modified urea resin performed polymer;

Wherein, the mass ratio of described urea, formaldehyde, trimeric cyanamide and formic acid is 1:1.3:0.05:0.01;

In sodium hydroxide solution, the massfraction of sodium hydroxide is 30%.

4. the additive of a kind of resol according to claim 1, it is characterised in that: described curing catalyst is more than one in sodium carbonate, glycerol acetate and propylene carbonate; Stablizer is more than one in SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, borax and Sodium Benzoate.

5. the preparation method of the additive of a resol as claimed in claim 1, it is characterised in that: described method steps is as follows:

(1) cake of camellia oleifera seeds powder is dispersed in water, adds linking agent and also stir evenly, obtain mixture a; By mixture a insulation reaction 2��3h at 50��70 DEG C, obtain mixture b;

(2) mixture b is cooled to 30 DEG C, adds curing catalyst and stablizer, stir evenly and insulation reaction 0.5��1h, obtain the additive of described resol.

6. the application of the additive of a resol as claimed in claim 1, it is characterized in that: described additive is used in phenolic resin adhesive, phenolic resin adhesive is made up of additive and resol, wherein, resol is solid content is 40��50%, and apparent viscosity is the heat-reactive phenolic resin of 150��1500 centipoises; The mass ratio of additive and resol is 20��30:100.