CN101519572A - Method for preparing phenol formaldehyde adhesive by bio oil - Google Patents

Abstract

The invention relates to a method for preparing phenol formaldehyde adhesive by bio oil, which belongs to the technical field of the wood adhesive. The method comprises the following steps: phenol, formaldehyde, sodium hydroxide solution, and the like are weighted according to the mol ratio, the bio oil is weighted, 50 percent of weighted phenol, the weighted bio oil, the weighted sodium hydroxide solution and sodium carbonate are put in a reaction kettle for heating and reaction, the weighted formaldehyde is added in the reaction kettle, and temperature rising and heat preserving step by step as well as sampling and viscosity measuring are performed. When the viscosity satisfies the requirement, the temperature is reduced and the phenol formaldehyde adhesive is prepared. The method is characterized in that agriculture and forestry remainder rapid pyrogenation bio oil with low cost is adopted to replace parts of phenol to prepare phenolic resin, thereby the production cost of the phenolic resin is greatly lowered, and biomass energy sources such as agriculture and forestry remainder, and the like are efficiently recycled.

Description

A kind of method for preparing synvaren with bio oil

Technical field

The present invention relates to a kind ofly prepare the method for synvaren, belong to the wood adhesive technical field with bio oil.

Background technology

Tackiness agent is as the important source material of wood materials production of articles such as wood-based plate, for the performance that improves the wood materials goods, reduce the wooden material production cost and enlarge its use range all significant.At present, global wood adhesive output has accounted for 3/4 of tackiness agent ultimate production.Along with the development of modern timber processing industry, not only consumption enlarges wood adhesive day by day, kind increases, and its consumption has become the important symbol of weighing a country or a regional timber industry state-of-art.

It mainly is that wood-based plate manufacturing and woodwork are produced two big fields that China's wood working is used tackiness agent.The aldehyde adhesive stick: urea-formaldehyde resin adhesive, Phenol aldehyde resin and melamine formaldehyde resin glue are that wood-based panel industry is used three maximum big synthetical glue kinds.Distinguish by different purposes, make protection against the tide level and accurate water-fast level wood-based plate use trimeric cyanamide-urea cocondensation resin adhesive; Resol and isocyanate adhesive are used in the manufacturing of waterproof construction class wood-based plate; Glueing joint the timber manufacturing uses the aqueous macromolecule-isocyanate tackiness agent or uses the resorcinol formaldehyde resin tackiness agent; The wood-based plate surface decoration mainly uses melamine resin with material; The furniture manufacturing is extensive use of polyvinyl acetate emulsion adhesive (white glue with vinyl), ethene-vinyl acetate copolymer resins (EVA) hot melt adhesive; The sheet material clad can uses Vinyl Acetate Copolymer-urea-formaldehyde resin, chloroprene rubber; As the suitable wood-based plate edge sealing of wet environments such as kitchen, for the water-fast vapour aging resistance that improves hot melt adhesive uses reactive hot-melt adhesive.

Resol was the macromolecular compound of first synthetic, is carried out in alkali or acidic medium by phenol and formaldehyde that polycondensation forms, and just was used to wood gluing as far back as 1909.At present, timber sticks with glue agent mainly based on " three aldehyde " glue, accounts for whole timber and wood-based panel industry and sticks with glue more than 80% of agent, and in " three-aldehyde glue ", Phenol aldehyde resin is that the second largest timber that is only second to the urea-formaldehyde resin adhesive consumption sticks with glue agent.It has excellent Joint strength, excellent water tolerance, thermotolerance and chemical stability, is the main glue kind of present outdoor use wood-based plate.Yet the tackiness agent that timber industry is used is urea-formaldehyde resin adhesive more than 80%, and the consumption of Phenol aldehyde resin is less, and major cause is to make that raw material-phenol costs an arm and a leg and the urea price is comparatively cheap; Set time is long, temperature is high, has influenced the production efficiency of artificial board product line.In addition, contain free phenol, free aldehyde in the synvaren, can influence HUMAN HEALTH if burst size exceeds standard.

Therefore, reduce the synvaren production cost, improve its eco-environmental prote and become the wood adhesive industry and be badly in need of one of key problem that solves.

Summary of the invention

The objective of the invention is to propose a kind of method for preparing synvaren with bio oil, in order to solve synvaren production cost height, problem that eco-environmental prote is not good enough, substitute the component that has in the wood adhesive with bio oil, and change preparation technology, reducing the production cost of wood adhesive greatly, and biomass resource is efficiently utilized.

What the present invention proposed prepares the method for synvaren with bio oil, may further comprise the steps:

(1) following each component is pressed following molar ratio weighing:

Phenol 1

Formaldehyde 1.6～2.0

Aqueous sodium hydroxide solution 0.25～0.45;

(2) weighing bio oil, the weight of bio oil are 50% of above-mentioned weighing phenol weight;

(3) get above-mentioned weighing phenol 50%, the aqueous sodium hydroxide solution and the yellow soda ash of the bio oil of above-mentioned weighing, above-mentioned weighing puts into the reactor reacting by heating, be warming up to 40～45 ℃ in 10～15 minutes, wherein, the add-on of yellow soda ash be 50% weighing phenol, weighing bio oil, weighing formaldehyde and weighing aqueous sodium hydroxide solution summation 2～4%;

(4) in aforesaid reaction vessel, add 60%～80% of above-mentioned weighing formaldehyde, in 40～50 minutes, be warming up to 70～80 ℃, be incubated after 20 minutes, in 10 minutes, be warming up to 90～95 ℃ again, be incubated 10 minutes, continue to be cooled to 55～65 ℃, add remaining weighing formaldehyde, 10～20 minutes internal heating to 80～95 ℃, sampling, measure viscosity down at 23 ℃, when the viscosity in the time of 23 ℃ is 65～90 seconds, be cooled to 25～35 ℃ of dischargings.

What the present invention proposed prepares the method for synvaren with bio oil, adopt cheap agricultural residuum fast pyrogenation bio oil partly to substitute phenol and prepare resol, the one-tenth that can greatly reduce resol produces cost, and the preparation method who is invented can improve the eco-environmental prote of resol under the prerequisite that guarantees its bonding strength.

Compare with existing similar technology, the present invention has the following advantages and beneficial effect:

1. the bio oil that adopts cheap agricultural residuum to carry out the fast pyrogenation generation partly substitutes (50% substitution rate) phenol and prepares the biological oil-phenolic resin tackiness agent, can reduce the production cost of synvaren significantly.Generally speaking, the resol that can make under the 50% substitution rate condition 1000～2000/t that reduces cost.

2. substitute phenol, control the content that parameters such as mol ratio, reaction times and temperature can be controlled free phenol and free aldehyde by part, thereby improve the eco-environmental prote of biological oil-phenolic resin.

3. it is synthetic that the composite catalyst system that adopts sodium hydroxide and sodium carbonate to constitute carries out resin, accelerates the synthetic polymerization rate.Make hot pressing temperature reduction, the curing reaction time of the use of biological oil-phenolic resin tackiness agent shorten.

4. by preparation biological oil-phenolic resin tackiness agent, make biomass energy resource such as agricultural residuum obtain the efficient circulation utilization.

Embodiment

What the present invention proposed prepares the method for synvaren with bio oil, may further comprise the steps:

(1) following each component is pressed following molar ratio weighing:

Phenol 1

Formaldehyde 1.6～2.0

Aqueous sodium hydroxide solution 0.25～0.45;

(2) weighing bio oil, the weight of bio oil are 50% of above-mentioned weighing phenol weight;

(3) get above-mentioned weighing phenol 50%, the aqueous sodium hydroxide solution and the yellow soda ash of the bio oil of above-mentioned weighing, above-mentioned weighing puts into the reactor reacting by heating, be warming up to 40～45 ℃ in 10～15 minutes, wherein, the add-on of yellow soda ash be 50% weighing phenol, weighing bio oil, weighing formaldehyde and weighing aqueous sodium hydroxide solution summation 2～4%;

(4) in aforesaid reaction vessel, add 60%～80% of above-mentioned weighing formaldehyde, in 40～50 minutes, be warming up to 70～80 ℃, be incubated after 20 minutes, in 10 minutes, be warming up to 90～95 ℃ again, be incubated 10 minutes, continue to be cooled to 55～65 ℃, add remaining weighing formaldehyde, 10～20 minutes internal heating to 80～95 ℃, sampling, measure viscosity down at 23 ℃, when the viscosity in the time of 23 ℃ is 65～90 seconds, be cooled to 25～35 ℃ of dischargings.

Be to contain a large amount of plant polyphenol compounds in the bio oil of raw material production with agricultural residuum etc., and production cost is lower, substitute the needed phenol of preparation synvaren with its part, not only can reduce the cost of synvaren significantly, and can realize Sustainable utilization of resources, meet the strategic requirement of China's sustainable development.The biological oil-phenolic resin tackiness agent has the free phenol littler than common resol, and environmental protection does not damage HUMAN HEALTH.

What the present invention proposed prepares the method for synvaren with bio oil, be to utilize the characteristics that are rich in plant polyphenol in the bio oil, do not needing directly all to utilize alternative part phenol under the purified condition, adopt the composite catalyst of metal-salt, can promote the speed and the degree of bio oil-P-F copolycondensation, improve the bio oil substitution rate.By substituting the use properties that parameters such as part phenol, control mol ratio, reaction times and temperature, the number of times that feeds intake can guarantee the biological oil-phenolic resin tackiness agent, the content of control free phenol and free aldehyde, thereby the eco-environmental prote of raising biological oil-phenolic resin.

Below introduce the embodiment of the inventive method:

Embodiment 1

Table 1: the biological oil-phenolic resin adhesive formulation of example 1

Raw material	Purity (%)	Mol ratio	Weight (gram)
				Phenol	100	0.5	50
Bio oil (full oil utilizes)	100	——	50
				Formaldehyde	37	1.7	147
Aqueous sodium hydroxide solution	40	0.3	32
				Yellow soda ash	100	——	6

Fast pyrolysis processes cotton stalk refining bio oil on spouted circulating fluid bed rapid pyrolysis apparatus, the yield of bio oil are 65% (with the ratio of the weight of biomass material).Take by weighing purified petroleum benzin phenol 50 gram, cotton stalk bio oil 50 grams, mass concentration respectively and be 37% formalin 147 grams, mass concentration and be 40% aqueous sodium hydroxide solution 32 grams, anhydrous sodium carbonate 6 grams.Phenol, bio oil, aqueous sodium hydroxide solution, yellow soda ash are all dropped into reaction kettle for reaction, temperature rise to 40 in 10 minutes～45 ℃.In system, add the formaldehyde of 103 grams, be warming up to 80～85 ℃ in 45 minutes, be incubated after 20 minutes, in 10 minutes, reactant is heated to 90～95 ℃, under this state, kept 15 minutes.Be cooled to 55～60 ℃, add residual formaldehyde, then at 10～15 minutes internal heating to certain 85～95 ℃.Sampling and measuring viscosity in said process when reacting when viscosity is 65～75s, is cooled to 25～30 ℃ of dischargings.

Table 2: the biological oil-phenolic resin tackiness agent performance index of example 1

Index

Gummed is strong

Viscosity (s)

Solid contains

pH

Polymerization

Shelf lives

Free-phenol content

Free first

	Degree (MPa)		Amount (%)		Time (s)	(d)	(％)	Aldehyde (%)
									Numerical value	1.3	75	47.5	11	65	>25	0.150	0.035

Embodiment 2

Table 3: the biological oil-phenolic resin adhesive formulation of example 2

Raw material	Purity (%)	Mol ratio	Weight (gram)
				Phenol	100	0.5	50
Bio oil (full oil utilizes)	100	——	50
				Formaldehyde	37	1.9	164
Aqueous sodium hydroxide solution	40	0.35	38
				Yellow soda ash	100	——	9

Fast pyrolysis processes pinus sylvestris var. mongolica bark refining bio oil on the rotation conical rapid pyrolysis apparatus, the yield of bio oil are 65% (with the ratio of the weight of biomass material).Take by weighing purified petroleum benzin phenol 50 gram, pinus sylvestris var. mongolica bio oil 50 grams, mass concentration respectively and be 37% formalin 164 grams, mass concentration and be 40% aqueous sodium hydroxide solution 38 grams, anhydrous sodium carbonate 9 grams.Phenol, bio oil, aqueous sodium hydroxide solution, yellow soda ash are dropped into reaction kettle for reaction simultaneously, temperature rise to 40 in 10 minutes～45 ℃.In system, add the formaldehyde of 131 grams, be warming up to 80～85 ℃ in 45 minutes, be incubated after 20 minutes, in 10 minutes, reactant is heated to 90～95 ℃, under this state, kept 15 minutes.Be cooled to 50～55 ℃, add residual formaldehyde, then at 15～20 minutes internal heating to certain 85～95 ℃.Sampling and measuring viscosity in said process when reacting when viscosity is 70～80s, is cooled to 25～30 ℃ of dischargings.

Table 4: the biological oil-phenolic resin tackiness agent performance index of example 2

Index	Bonding strength (MPa)	Viscosity (s)	Solids content (%)	pH	Polymerization time (s)	Shelf lives (d)	Free-phenol content (%)	Free formaldehyde content (%)
									Numerical value	1.4	80	49.6	11	75	>30	0.180	0.025

Claims (1)

1, a kind ofly prepare the method for synvaren, it is characterized in that this method may further comprise the steps with bio oil:

(1) following each component is pressed following molar ratio weighing:

Phenol 1

Formaldehyde 1.6～2.0

Aqueous sodium hydroxide solution 0.25～0.45;

(2) weighing bio oil, the weight of bio oil are 50% of above-mentioned weighing phenol weight;

(3) get above-mentioned weighing phenol 50%, the aqueous sodium hydroxide solution and the yellow soda ash of the bio oil of above-mentioned weighing, above-mentioned weighing puts into the reactor reacting by heating, be warming up to 40～45 ℃ in 10～15 minutes, wherein, the add-on of yellow soda ash be 50% weighing phenol, weighing bio oil, weighing formaldehyde and weighing aqueous sodium hydroxide solution summation 2～4%;

(4) in aforesaid reaction vessel, add 60%～80% of above-mentioned weighing formaldehyde, in 40～50 minutes, be warming up to 70～80 ℃, be incubated after 20 minutes, in 10 minutes, be warming up to 90～95 ℃ again, be incubated 10 minutes, continue to be cooled to 55～65 ℃, add remaining weighing formaldehyde, 10～20 minutes internal heating to 80～95 ℃, sampling, measure viscosity down at 23 ℃, when the viscosity in the time of 23 ℃ is 65～90 seconds, be cooled to 25～35 ℃ of dischargings.