Gradient copolymer, its production and application thereof

Patent metadata

Field	Value
Publication number	US-11028334-B2
Application number	US-201716313869-A
Country	US
Kind code	B2
Filing date	Jun 27, 2017
Priority date	Jun 28, 2016
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

Abstract

A gradient copolymer comprises or consists of n polymer components. The n polymer components each independently represents an addition polymer of a monomer of the formula (I),and/or a mixture thereof, orthe n polymer components each independently comprises or consists essential of one or more structural units represented by the formula (I-1),The symbol n represents an integer within the closed interval [5, ∞]. The average side chain carbon number of the i-th polymer component as determined according to the nuclear magnetic resonance method is expressed as Xi, with the symbol i representing an arbitrary integer from 1 to n, the relationship X1<X2< . . . <Xn−1<Xn holds.

First claim

The invention claimed is:

1. A gradient copolymer comprising or consisting of a plurality of polymer components, wherein each of the plurality polymer components independently is an addition polymer of a monomer of formula (I), and/or a mixture of monomers of formula (I),

or
each of the plurality of polymer components independently comprises or consists essentially of one or more structural units of formula (I-1),

wherein a total number of the plurality of polymer components is n, and n is an integer within the closed interval [5, ∞], and in formula (I) or formula (I-1),
the group R 1 is H or

the group R 2 is H or a C 1-4 linear or branched alkyl,
a is 0 or 1,
the group R′ is H or a group R 3 ,
the group R 3 is a C 1 -C 30 linear or branched alkyl group, and
wherein an average number of carbon atoms in side chain of the i-th polymer component, as determined by nuclear magnetic resonance, is X i , wherein i is an integer from 1 to n, and X 1 <X 2 < . . . <X n−1 <X n ,
wherein a weight percentage of the i-th polymer component relative to a total weight of the plurality of polymer components is Y i , and Y 1 <Y 2 < . . . <Y j > . . . >Y n−1 >Y n ,
wherein j is an integer within the closed interval [(n+1)/4, 3(n+1)/4], and
Y 1 +Y 2 + . . . +Y i + . . . +Y n−1 +Y n =100%,
wherein Y i and X i satisfy the following relationship,

Y
i

=

f
⁡

(

X
i

)

=

1

2
⁢
π

⁢
σ

⁢

e

-

(

X
i

-
μ

)

2

2
⁢

σ
2

,

(
IV
)

wherein μ is a value within the open interval (12.5, 14.2), and σ is a value within the open interval (0.5, 2).

2. The gradient copolymer according to claim 1 , wherein the gradient copolymer has an average number of carbon atoms in side chain, as determined by nuclear magnetic resonance, within a range from 5 to 20, or the number average molecular weight Mn of the plurality of polymer components or the gradient copolymer is each independently from 10,000 to 1,000,000, or the molecular weight distribution Mw/Mn of the plurality of polymer components or the gradient copolymer is each independently from 1.8 to 3.5.

3. The gradient copolymer according to claim 1 , wherein the monomer of formula (I) is one or more selected from the group consisting of C 6 linear alkyl (meth)acrylates, C 8 linear alkyl (meth)acrylates, C 10 linear alkyl (meth)acrylates, C 12 linear alkyl (meth)acrylates, C 14 linear alkyl (meth)acrylates, C 16 linear alkyl (meth)acrylates, C 18 linear alkyl (meth)acrylates, and C 20 linear alkyl (meth)acrylates.

4. The gradient copolymer according to claim 1 , wherein a proportion (by mole) of the one or more structural units of formula (I-1), in which the group R 3 is a C 10 -C 18 linear or branched alkyl group, relative to the total amount of the structural units constituting each of the plurality of polymer components, is from 40% to 95%.

5. The gradient copolymer according to claim 1 , wherein said X 1 is a value within the closed interval [6.5, 12.5], or said X n is a value within the closed interval [13.8, 19.5].

6. The gradient copolymer according to claim 1 , wherein said Y j is within a range from 20% to 75%, or said Y 1 or Y n is within a range from 0.01% to 20%.

7. A method for producing the gradient copolymer according to claim 1 , comprising:
adding at least two monomers to a polymerization system, and conducting an addition copolymerization of the at least two monomers, wherein the at least two monomers each independently is a compound of formula (I),

and
in formula (I),
the group R 1 is H or

the group R 2 is H or a C 1-4 linear or branched alkyl,
a is 0 or 1,
the group R′ is H or a group R 3 ,
the group R 3 is a C 1 -C 30 linear or branched alkyl group, and
wherein the starting time of adding the at least two monomers to the polymerization system is t 0 , and the termination time is t m , the addition time of the at least two monomers is t and t=t m −t 0 , and wherein the addition time is divided into m segments, m is an integer within the closed interval [5, ∞],
wherein, during the addition of the at least two monomers, a ratio between the at least two monomers added to the polymerization system at any moment of time t x , the symbol x representing an integer from 0 to m, varies such that the average number of carbon atoms in side chain X x of a resulting mixture composed of the at least two monomers as determined by nuclear magnetic resonance satisfies the following relationship,
X 0 <X 1 < . . . <X m−1 <X m .

8. The production method according to claim 7 , wherein, at the terminati

Assignees

• China Petroleum & Chem Corp
• Sinopec Res Inst Petroleum

Inventors

• Zhang Yao
• Duan Qinghua
• Wei Kecheng
• Liu Yinong
• Sun Hongwei

Classifications

• C08F220/1811

  C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate · CPC title

• C10M2203/003

  used as base material · CPC title

• C10M169/041

  the additives being macromolecular compounds only · CPC title

• C08F220/1818

  C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate · CPC title

• C08F220/1812

  C12-(meth)acrylate, e.g. lauryl (meth)acrylate · CPC title