CN109134839A - A kind of preparation of hyperbranched type paraffin and its application in wood-based plate - Google Patents
A kind of preparation of hyperbranched type paraffin and its application in wood-based plate Download PDFInfo
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- CN109134839A CN109134839A CN201811023893.6A CN201811023893A CN109134839A CN 109134839 A CN109134839 A CN 109134839A CN 201811023893 A CN201811023893 A CN 201811023893A CN 109134839 A CN109134839 A CN 109134839A
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- Prior art keywords
- paraffin
- hyperbranched
- generation
- wood
- based plate
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- 239000012188 paraffin wax Substances 0.000 title claims abstract description 50
- 239000002023 wood Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000010526 radical polymerization reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003999 initiator Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 230000002045 lasting effect Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 9
- 229940043237 diethanolamine Drugs 0.000 description 9
- 229940014800 succinic anhydride Drugs 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000004078 waterproofing Methods 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 229940031098 ethanolamine Drugs 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/02—Mixing the material with binding agent
- B27N1/0209—Methods, e.g. characterised by the composition of the agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/08—Moulding or pressing
- B27N3/10—Moulding of mats
- B27N3/12—Moulding of mats from fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Forests & Forestry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The present invention relates to wood-based plate field, more specifically to a kind of hyperbranched type paraffin preparation and its application in wood-based plate.A kind of Hyperbranched Polymer with Terminal Hydroxyl has been synthesized first, then by the way that double bond is introduced into the dissaving polymer end with acrylic acid modified, to synthesize a kind of terminal double bond dissaving polymer.The end group is the dissaving polymer of double bond under the action of initiator and paraffin polymerize to obtain hyperbranched type paraffin there is good waterproof effect, and stability is good, effect is lasting, synthesis technology is easy, easily industrializes, is a kind of artificial board waterproof agent of function admirable.
Description
Technical field
It is the present invention relates to artificial board technology field, in particular to a kind of for improving the over-expense fossil of wood-based plate water resistance
Wax further relates to preparation method.
Background technique
With the development and the improvement of people's living standards of home furnishings market, the positive diversification hair of floor decorative material
Exhibition.The features such as wood-based plate is beautiful, wear-resisting, practical with it, easy cleaning is used to manufacture with billboard signboard, floor, tables and chairs, label
Board, toilet decoration, transportation box, building template, vehicle interior finishing, shop fronts decoration etc..Therefore to the items of wood-based plate
The requirement of physical and mechanical property, especially waterproof performance is also higher and higher.It is well known that using plant fiber as people made of raw material
Plate is made, still has the characteristics that mushy between binding site, the deformation, swollen of wood-based plate will be caused after moisture absorption, water suction
Swollen and decrease intensity, to influence its application range and service life.In order to reduce moisture absorption, the water imbibition of wood-based plate, improve anti-
Water effect must just add hydrophobic substance in building board production process, and the most common waterproofing agent of enterprise is paraffin at present.
For the waterproof principle, belong to a kind of physical phenomenon for obstructing hole between fiber, additive amount is excessively unfavorable for fiber and fibre
Binding strength between dimension.It is reacted according to wood-based plate producer, making waterproofing agent with paraffin causes the waterproof effect of wood-based plate unstable.
The invention patent is intended to introduce the hyperbranched graft polymerization paraffin for containing a large amount of active group, so that paraffin is more
Uniform fine and close is coated on each wood-fibred particle, and then improves its waterproof performance.
Dissaving polymer has 3 D stereo reticular structure, and active site is more, and viscosity is small, good with matrix amalgamation, tool
Have broad application prospects, is all shown in fields such as photoelectric material, coating, adhesive, nanosecond science and technology, drug carriers at present
Huge application value.
Summary of the invention
In order to solve the problems such as wood-based plate waterproofness is bad, the present invention provides a kind of for improving paraffin waterproof performance
Dissaving polymer.
The present invention also provides the preparation methods of the dissaving polymer.
The present invention is achieved by the following measures:
A kind of preparation for overspending fossil waxes and its application in wood-based plate, it is characterised in that the dissaving polymer branch last-in-chain(LIC)
End contains a large amount of double bond.
What the dissaving polymer was obtained through the following steps:
(1)AB2The synthesis of monomer
The succinic anhydride and diethanol amine of equimolar amounts react, as follows:
(2) synthesis of Hyperbranched Polymer with Terminal Hydroxyl
Core molecule trimethylolpropane and AB2Monomer reaction, as follows:
(3) Hyperbranched Polymer with Terminal Hydroxyl is reacted with acrylic acid
Wherein, intermediate circle represents dissaving polymer, and-OH indicates that the terminal hydroxy group of dissaving polymer, superbrnaching end-hydroxy are poly-
It closes after object is reacted with acrylic acid and obtains the dissaving polymer of double bond sealing end.
(4) hyperbranched propenoic acid and paraffin are under the action of initiator B PO, synthesis of super branched type paraffin
。
The Hyperbranched Polymer with Terminal Hydroxyl, the first generation, the second generation, the third generation, forth generation difference algebra core molecule and AB2
The molar ratio of monomer is respectively 1:3,1:9,1:21,1:45.
The end group is the dissaving polymer of double bond, the first generation, the second generation, the third generation, forth generation difference algebraic kernel point
The molar ratio of son and acrylic acid is 1:6,1:12,1:24,1:48.
The hyperbranched type paraffin, the first generation, the second generation, the third generation, forth generation difference algebra end group are the over-expenses of double bond
The molar ratio of fluidized polymer and paraffin is 1:12,1:24,1:48,1:96.
Paraffin is added in artificial board shaping and makees waterproofing agent, paraffin particles cannot be uniformly coated on if paraffin additive amount is low
On wood-fibred, if the bond strength that adding too much will lead to wood-based plate substantially reduces.So present invention introduces containing a large amount of
The dissaving polymer of active group, so that a small amount of paraffin, which is added, both can achieve the waterproof effect of national standard, also not shadow
Its bond strength is rung, and then improves its comprehensive performance, and since dissaving polymer has 3 D stereo reticular structure, branch
More, active site is more, and introducing polar group can be good in conjunction with urea-formaldehyde glue, fundamentally solves the problems, such as its waterproof.
Beneficial effects of the present invention:
It is unstable that the dissaving polymer that the present invention is used as waterproofing agent can significantly improve wood-based plate waterproof effect, while wood-based plate
Physical property influence smaller, function admirable, be that a kind of stability is good, effect is lasting, and synthesis technology is simple, convenient for industrial metaplasia
The waterproofing agent of production has good market development prospect.
Specific embodiment
More to be stated in detail to specific implementation method of the present invention below, it is therefore intended that illustrate design of the invention and
Feature, it is not intended to limit the scope of the present invention.Any equivalent change or modification in accordance with the spirit of the invention,
It should be covered by the protection scope of the present invention.
Implementation method one
(1) 45.032g(0.45mol is weighed) succinic anhydride, 47.313g(0.45mol) diethanol amine, diethanol amine is added first
Enter in the three-necked flask with magnetic stirring apparatus, then the appropriate DMAc of succinic anhydride is dissolved；Then it puts it into and is mounted on two
In dropping funel on the there-necked flask of ethanol amine, is stirred when being added dropwise, drip and temperature is risen into 40 DEG C of reaction 12h, reaction
Product is AB2Type monomer.160 mL toluene (toluene is water entrainer) is first added in the above system, adds 20.126g
(0.15mol) trimethylolpropane is added 0.500g p-methyl benzenesulfonic acid and makees catalyst as core molecule；Then it begins to warm up, directly
To boiling, there is reflux to generate in spherical condensation tube, temperature is risen into 140 DEG C of reaction 8h and obtains the hyperbranched polymerization that end is hydroxyl
Object solution.Then 64.854 g(0.90mol are weighed) acrylic acid, 0.889g p-methyl benzenesulfonic acid, p-methyl benzenesulfonic acid is added first
In the dissaving polymer system of the terminal hydroxy group prepared to previous step, then acrylic acid is poured into dropping funel and is slowly dropped to
In the dissaving polymer of the terminal hydroxy group of previous step preparation, is stirred when being added dropwise, react 6h at 80 DEG C after completion of dropwise addition, then
The solvent being evaporated under reduced pressure in removing system obtains the dissaving polymer that end is double bond.
(2) 70.152g paraffin, the hyperbranched type acrylic acid of 25.255g are added in four-hole boiling flask, is heated to 65 DEG C of fusings and stirs
It mixes, then heats to 85 DEG C of addition initiator B PO, react 4h to get paraffin and be grafted dissaving polymer crude product.It will with acetone
Product precipitation and separation is repeatedly washed, dry to constant weight, obtains modified paraffin fine work.
(3) take wood-fibred, urea-formaldehyde glue and 3 ~ 12% modified paraffin investment reaction kettle in mix, then discharge is in temperature
165 DEG C, pressure is to form after hot pressing 10min under 15MPa, obtains water resistance wood-based plate.
Implementation method two
(1) 45.032g(0.45mol is weighed) succinic anhydride, 47.313g(0.45mol) diethanol amine, diethanol amine is added first
Enter in the three-necked flask with magnetic stirring apparatus, then the appropriate DMAc of succinic anhydride is dissolved；Then it puts it into and is mounted on two
In dropping funel on the there-necked flask of ethanol amine, is stirred when being added dropwise, drip and temperature is risen into 40 DEG C of reaction 12h, reaction
Product is AB2Type monomer.160 mL toluene (toluene is water entrainer) is first added in the above system, adds 6.709g
(0.05mol) trimethylolpropane is added 0.500g p-methyl benzenesulfonic acid and makees catalyst as core molecule；Then it begins to warm up, directly
To boiling, there is reflux to generate in spherical condensation tube, temperature is risen into 140 DEG C of reaction 8h and obtains the hyperbranched polymerization that end is hydroxyl
Object solution.Then 43.236 g(0.60mol are weighed) acrylic acid, 0.778g p-methyl benzenesulfonic acid, p-methyl benzenesulfonic acid is added first
In the dissaving polymer system of the terminal hydroxy group prepared to previous step, then acrylic acid is poured into dropping funel and is slowly dropped to
In the dissaving polymer of the terminal hydroxy group of previous step preparation, is stirred when being added dropwise, react 6h at 80 DEG C after completion of dropwise addition, then
The solvent being evaporated under reduced pressure in removing system obtains the dissaving polymer that end is double bond.
(2) 70.152g paraffin, the hyperbranched type acrylic acid of 25.255g are added in four-hole boiling flask, is heated to 65 DEG C of fusings and stirs
It mixes, then heats to 85 DEG C of addition initiator B PO, react 4h to get paraffin and be grafted dissaving polymer crude product.It will with acetone
Product precipitation and separation is repeatedly washed, dry to constant weight, obtains modified paraffin fine work.
(3) take wood-fibred, urea-formaldehyde glue and 3 ~ 12% modified paraffin investment reaction kettle in mix, then discharge is in temperature
165 DEG C, pressure is to form after hot pressing 10min under 15MPa, obtains water resistance wood-based plate.
Implementation method three
(1) 45.032g(0.45mol is weighed) succinic anhydride, 47.313g(0.45mol) diethanol amine, diethanol amine is added first
Enter in the three-necked flask with magnetic stirring apparatus, then the appropriate DMAc of succinic anhydride is dissolved；Then it puts it into and is mounted on two
In dropping funel on the there-necked flask of ethanol amine, is stirred when being added dropwise, drip and temperature is risen into 40 DEG C of reaction 12h, reaction
Product is AB2Type monomer.160 mL toluene (toluene is water entrainer) is first added in the above system, adds 2.952g
(0.022mol) trimethylolpropane is added 0.500g p-methyl benzenesulfonic acid and makees catalyst as core molecule；Then it begins to warm up, directly
To boiling, there is reflux to generate in spherical condensation tube, temperature is risen into 140 DEG C of reaction 8h and obtains the hyperbranched polymerization that end is hydroxyl
Object solution.Then 36.030 g(0.50mol are weighed) acrylic acid, 0.742g p-methyl benzenesulfonic acid, p-methyl benzenesulfonic acid is added first
In the dissaving polymer system of the terminal hydroxy group prepared to previous step, then acrylic acid is poured into dropping funel and is slowly dropped to
In the dissaving polymer of the terminal hydroxy group of previous step preparation, is stirred when being added dropwise, react 6h at 80 DEG C after completion of dropwise addition, then
The solvent being evaporated under reduced pressure in removing system obtains the dissaving polymer that end is double bond.
(2) 70.152g paraffin, the hyperbranched type acrylic acid of the 25.255g second generation are added in four-hole boiling flask, is heated to 65 DEG C
Fusing stirring, then heats to 85 DEG C of addition initiator B PO, reacts 4h to get paraffin and is grafted dissaving polymer crude product.With
Acetone repeatedly washs product precipitation and separation, dry to constant weight, obtains modified paraffin fine work.
(3) take wood-fibred, urea-formaldehyde glue and 3 ~ 12% modified paraffin investment reaction kettle in mix, then discharge is in temperature
165 DEG C, pressure is to form after hot pressing 10min under 15MPa, obtains water resistance wood-based plate.
Implementation method four
(1) 45.032g(0.45mol is weighed) succinic anhydride, 47.313g(0.45mol) diethanol amine, diethanol amine is added first
Enter in the three-necked flask with magnetic stirring apparatus, then the appropriate DMAc of succinic anhydride is dissolved；Then it puts it into and is mounted on two
In dropping funel on the there-necked flask of ethanol amine, is stirred when being added dropwise, drip and temperature is risen into 40 DEG C of reaction 12h, reaction
Product is AB2Type monomer.160 mL toluene (toluene is water entrainer) is first added in the above system, adds 1.342g
(0.01mol) trimethylolpropane is added 0.500g p-methyl benzenesulfonic acid and makees catalyst as core molecule；Then it begins to warm up, directly
To boiling, there is reflux to generate in spherical condensation tube, temperature is risen into 140 DEG C of reaction 8h and obtains the hyperbranched polymerization that end is hydroxyl
Object solution.Then 28.824 g(0.40mol are weighed) acrylic acid, 0.698g p-methyl benzenesulfonic acid, p-methyl benzenesulfonic acid is added first
In the dissaving polymer system of the terminal hydroxy group prepared to previous step, then acrylic acid is poured into dropping funel and is slowly dropped to
In the dissaving polymer of the terminal hydroxy group of previous step preparation, is stirred when being added dropwise, react 6h at 80 DEG C after completion of dropwise addition, then
The solvent being evaporated under reduced pressure in removing system obtains the dissaving polymer that end is double bond.
(2) 70.152g paraffin, the hyperbranched type acrylic acid of the 25.255g second generation are added in four-hole boiling flask, is heated to 65 DEG C
Fusing stirring, then heats to 85 DEG C of addition initiator B PO, reacts 4h to get paraffin and is grafted dissaving polymer crude product.With
Acetone repeatedly washs product precipitation and separation, dry to constant weight, obtains modified paraffin fine work.
(3) take wood-fibred, urea-formaldehyde glue and 3 ~ 12% modified paraffin investment reaction kettle in mix, then discharge is in temperature
165 DEG C, pressure is to form after hot pressing 10min under 15MPa, obtains water resistance wood-based plate.
The present invention by taking second generation dissaving polymer as an example, first generation dissaving polymer, third generation dissaving polymer,
Forth generation dissaving polymer modified paraffin and so on.
Performance test
It is below exactly that the hyperbranched type of addition obtained in implementation method of the present invention is modified in order to illustrate actual effect of the invention
Paraffin and the wood-based plate being prepared into are evaluated hyperbranched type modified paraffin and are made according to GB/T 11718-2009 " medium density fibre board (MDF) "
For the effect of waterproofing agent.
It in this test, is tested by taking the hyperbranched type paraffin of the second generation as an example, test performance is respectively such as the following table 1.
The hyperbranched type paraffin of 1 different content of table influences wood-based plate performance
| The additive amount of hyperbranched type paraffin | Thickness swelling rate/% | Bond strength/MPa |
| 0% | 20 | 0.9 |
| 3% | 11 | 0.8 |
| 6% | 9 | 0.8 |
| 9% | 9.5 | 0.8 |
| 12% | 10 | 0.7 |
As shown in Table 1, after adding the made hyperbranched type paraffin of the present invention, the wood-based plate ratio prepared is not added with modified paraffin
Waterproof performance make moderate progress；And when the additive amount of hyperbranched type paraffin is 6%, the comprehensive performance of wood-based plate is best.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the limit of embodiment
System, other any changes made without departing from the spirit and principles of the present invention, modification, combination, substitution, simplification should be
Equivalence replacement mode, is included within the scope of the present invention.
Claims (6)
1. a kind of preparation of hyperbranched type paraffin and its application in wood-based plate, it is characterised in that the dissaving polymer branch
Chain end contains a large amount of paraffin.
2. application according to claim 1, it is characterised in that additive amount of the hyperbranched type paraffin as artificial board waterproof agent
It is the 3 ~ 12% of wood-based plate raw material gross mass.
3. application according to claim 1, it is characterised in that it is the hyperbranched poly of double bond that hyperbranched type paraffin, which is by end group,
It closes object free radical polymerization under the initiation of BPO and obtains the hyperbranched type acrylic acid of paraffin grafting.
4. application according to claim 1, it is characterised in that the structural formula of obtained hyperbranched type paraffin is as follows:
Wherein, intermediate circle represents it is of the invention synthesize in addition to hydroxylic moiety Hyperbranched Polymer with Terminal Hydroxyl.
5. the molar ratio of application according to claim 1, core molecule and acrylic acid is that 1:6,1:12,1:24,1:48 are obtained
The first generation, the second generation, the third generation, forth generation difference algebra hyperbranched type acrylic acid.
6. application according to claim 1, it is characterised in that end group is the first generation, the second generation, the third generation, the 4th of double bond
It is 1:12,1:24,1:48 or 1:96 for dissaving polymer and paraffin monomer mole ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811023893.6A CN109134839B (en) | 2018-09-04 | 2018-09-04 | Preparation of hyperbranched paraffin and application of hyperbranched paraffin in artificial board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811023893.6A CN109134839B (en) | 2018-09-04 | 2018-09-04 | Preparation of hyperbranched paraffin and application of hyperbranched paraffin in artificial board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109134839A true CN109134839A (en) | 2019-01-04 |
| CN109134839B CN109134839B (en) | 2020-12-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109705364A (en) * | 2019-02-18 | 2019-05-03 | 济南大学 | A kind of preparation and its application of hyperbranched silicone modified paraffin |
| CN109880014A (en) * | 2019-01-28 | 2019-06-14 | 济南大学 | The preparation and the application in wood-based plate of a kind of hyperbranched type silicone acrylate emulsion |
| CN114989364A (en) * | 2021-03-01 | 2022-09-02 | 中国石油化工股份有限公司 | Polyamine ester dendritic polymer and preparation method and application thereof |
| WO2022184023A1 (en) * | 2021-03-01 | 2022-09-09 | 中国石油化工股份有限公司 | Dendritic polymer, and preparation method therefor and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880014A (en) * | 2019-01-28 | 2019-06-14 | 济南大学 | The preparation and the application in wood-based plate of a kind of hyperbranched type silicone acrylate emulsion |
| CN109880014B (en) * | 2019-01-28 | 2021-08-03 | 济南大学 | Preparation of hyperbranched organic silicon-acrylate emulsion and application of hyperbranched organic silicon-acrylate emulsion in artificial board |
| CN109705364A (en) * | 2019-02-18 | 2019-05-03 | 济南大学 | A kind of preparation and its application of hyperbranched silicone modified paraffin |
| CN109705364B (en) * | 2019-02-18 | 2020-09-01 | 济南大学 | Preparation and application of hyperbranched organic silicon modified paraffin |
| CN114989364A (en) * | 2021-03-01 | 2022-09-02 | 中国石油化工股份有限公司 | Polyamine ester dendritic polymer and preparation method and application thereof |
| WO2022184023A1 (en) * | 2021-03-01 | 2022-09-09 | 中国石油化工股份有限公司 | Dendritic polymer, and preparation method therefor and application thereof |
| CN114989364B (en) * | 2021-03-01 | 2023-07-25 | 中国石油化工股份有限公司 | Polyurethane dendritic polymer and preparation method and application thereof |
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| CN109134839B (en) | 2020-12-22 |
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